tag:blogger.com,1999:blog-9080735588722514682024-02-06T19:39:41.823-08:00Molecular Electron Density Theory (MEDT) Prof. Luis R. Domingo - Dr. Mar Ríos Gutiérrez luisrdomingohttp://www.blogger.com/profile/00145107227339444002noreply@blogger.comBlogger1125tag:blogger.com,1999:blog-908073558872251468.post-5116817945508292062013-01-12T09:13:00.043-08:002023-08-14T14:39:15.587-07:00<div class="MsoNormal">
<div class="MsoNormal" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial;">
<div style="background-position: initial initial; background-repeat: initial initial; margin: 0cm 0cm 0.0001pt;">
<div class="MsoNormal" style="background-color: white; line-height: 200%; text-align: center;"><p class="MsoNormal" style="text-align: center;"><span style="color: #2b00fe; font-family: arial; font-size: large;"><b>Chemistry is not Physics</b></span></p><div style="text-align: center;"><div style="text-align: justify;"><span style="font-family: arial;"><span style="color: #2b00fe;">Chemistry
is an empirical science in which their hypotheses are confirmed by experiments.</span></span></div><span style="color: #2b00fe; font-family: arial;"><div style="text-align: justify;">Theoretical chemists verify their hypotheses through a series of theoretical
calculations based on quantum chemical models, which today allow a rigorous analysis of
molecular electron density.</div></span></div><p class="MsoNormal" style="text-align: center;"><span face="Arial, sans-serif" lang="EN-GB" style="line-height: 107%;"><span style="color: #2b00fe; font-size: large;"><b><br /></b></span></span></p><p class="MsoNormal" style="text-align: center;"><span face="Arial, sans-serif" lang="EN-GB" style="line-height: 107%;"><span style="color: #2b00fe; font-family: arial; font-size: large;"><b>The MEDT today</b></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">Dear Colleagues,</span><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">Six seven ago, in 2016, I published two relevant manuscripts: (a) Molecular
Electron Density Theory (MEDT): A Modern View of Reactivity in Organic
Chemistry (<i>Molecules</i> <b>2016</b>, <i>21</i>, 1319); and (b) Applications of the Conceptual
Density Functional Theory Indices to Organic Chemistry Reactivity (<i>Molecules
</i><b>2016</b>, <i>21</i>, 748).</span><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">In the first one, a new theory of reactivity in Organic Chemistry, i.e.
MEDT, was proposed in which the changes in electron density along a chemical
reaction, and not molecular orbital (MO) interactions as proposed K. Fukui’s
Frontier Molecular Orbital (FMO) Theory (Nobel Prize in Chemistry in 1981 R.
with R. Hoffman), are responsible for the chemical reactivity of organic molecules.</span><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; margin-left: 0cm; margin-right: -.05pt; margin-top: 0cm; margin: 0cm -0.05pt 0cm 0cm; mso-outline-level: 3; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">MEDT rejects all
theories, models, and interpretations based on MO analyses such as Hoffmann’s
symmetry rules, K. N. Houk’s distortion/interaction energy model, and F. M. <b><a href="https://www.blogger.com/blog/post/edit/908073558872251468/511681794550829206"><span style="color: black; font-weight: normal;">Bickelhaupt</span></a></b>’s activation
strain model.<b> </b></span><b><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></b></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">In the second one, I presented a revision of the most relevant theoretical
reactivity indices used in the study of organic reactivity, including the
electrophilicity w index, the nucleophilicity N index, and the Parr functions.
These reactivity indices, which are a powerful tool for experimental organic
chemists, play an important role in MEDT studies.</span><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span style="font-family: arial;"><span face="Arial, sans-serif" lang="EN-GB" style="font-size: 12pt; line-height: 150%;">Today, MEDT has been cited in 330 manuscripts, while the review of CDFT
indices has been cited in 810 manuscripts.</span><span lang="EN-GB" style="font-size: 12pt; line-height: 150%;"><o:p></o:p></span></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span lang="EN-GB" style="font-family: arial; font-size: 12pt; line-height: 150%;">If people recognized that by using the reactivity indices they are working
within the MEDT and cite it, the Houk’s and <a href="https://www.blogger.com/blog/post/edit/908073558872251468/511681794550829206"><span style="color: black;">Bickelhaupt</span></a>’s models based on MO interactions
would be widely rejected in organic chemistry and would be used only by
chemical physicists.<o:p></o:p></span></p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0cm; text-align: justify;"><span lang="EN-GB" style="font-family: arial; font-size: 12pt; line-height: 150%;"> </span></p><p class="MsoNormal" style="text-align: justify;">
</p><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0.0001pt; text-align: left;"><span lang="EN-GB" style="font-family: arial; font-size: 12pt; line-height: 150%;">Prof Luis R.
Domingo, FRSC</span><span lang="EN-GB" style="font-family: "Times New Roman", serif; font-size: 12pt; line-height: 150%;"><o:p></o:p></span></p><p class="MsoNormal"><br /></p></div><div class="MsoNormal" style="text-align: justify;"><div><div class="MsoNormal"><div style="background-color: white;"><div style="text-align: center;"><div style="line-height: 150%;"><h2>
<span face="" lang=""><span style="color: blue; font-family: arial; font-size: large; line-height: 150%;"><b>Molecular Electron Density Theory</b></span></span></h2>
</div>
</div>
<div style="text-align: center;">
<span style="font-family: arial;"><span face="" style="line-height: 24px;">A modern view of reactivity in Organic Chemistry</span><br />
<span face="" style="line-height: 24px;"><br /></span>
<span face="" style="line-height: 24px;"><span style="color: blue;"><b>Molecules</b> <b>2016, 21, 1319</b></span></span><br />
<span face="" style="color: blue;"><b><i><a href="http://www.mdpi.com/1420-3049/21/10/1319/pdf">download</a></i></b></span></span></div>
<span style="font-family: arial;"><span face="" style="line-height: 150%;"><br /></span>
<br />
</span><div class="MsoNormal" style="margin-bottom: 0.0001pt;">
<span style="font-family: arial;"><span face="" style="font-size: 12pt; line-height: 150%;">I am proposing a
new theory for the study of the reactivity organic reactions, named Molecular
Electron Density Theory (</span><b style="line-height: 150%;"><span face="" style="color: blue; font-size: 12pt; line-height: 150%;">MEDT</span></b><span face="" style="font-size: 12pt; line-height: 150%;">), which is based on the idea that<span class="apple-converted-space"> </span></span><span face="" style="font-size: 12pt; line-height: 150%;"><i><span style="line-height: 150%;">while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed Density Functional </span><span style="line-height: 24px;">Theory</span><span style="line-height: 150%;"> (DFT), the capability for changes in electron density, and not molecular orbital interactions, is responsible for molecular reactivity</span></i></span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><span face="" style="font-size: 12pt; line-height: 150%;">(</span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.<span class="apple-converted-space"> </span></i><b style="font-size: 12pt; line-height: 150%;">2014</b><i style="font-size: 12pt; line-height: 150%;">, 4,<span class="apple-converted-space"> </span></i><span face="" style="font-size: 12pt; line-height: 150%;">32415). Therefore, the reactivity in
organic chemistry cannot be characterised neither by a static energy nor by a
geometrical study of the corresponding stationary points, including the
transition state structures, but by a rigorous analysis of the molecular
electron density changes along the reaction path, as well as of the changes in
energi</span><span style="font-size: 12pt; line-height: 150%;"><a href="https://www.blogger.com/null" name="_GoBack" style="font-size: 12pt; line-height: 150%;"></a></span><span face="" style="font-size: 12pt; line-height: 150%;">es required to reach the transition state geometry
in order to explain experimental activation energies.</span><br />
<span face=""><br /></span>
<span face="">Studies
based on the </span><span face="" style="color: blue;"><b>MEDT</b></span><span face=""> make it possible to rule out outdated concepts developed within the
Molecular Orbital theory such as:</span><br />
</span><div class="MsoNormal">
<span style="font-family: arial;">- The pericyclic
mechanisms.</span></div>
<div class="MsoNormal">
<span lang=""><span style="font-family: arial;">- The rules of conservation of orbital symmetry.<o:p></o:p></span></span></div>
<div class="MsoNormal">
<span lang=""><span style="font-family: arial;">- The
Frontier Molecular Orbital Theory.<o:p></o:p></span></span></div>
<div class="MsoNormal">
<span lang="" style="font-family: arial;"><span face="">- The distortion/interaction
reactivity model</span>.<o:p></o:p></span></div>
<span style="font-family: arial;"><span face="" style="font-size: 12pt; line-height: 150%;">
</span><br />
</span><div class="MsoNormal">
<span style="font-family: arial;"><span face="" style="font-size: 12pt; line-height: 150%;">Most of our recent
theoretical studies devoted to relevant organic reactions such as Diels-Alder
reactions (</span><i style="font-size: 12pt; line-height: 150%;">Org. Biomol. Chem.</i><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2009</b><span face="" style="font-size: 12pt; line-height: 150%;">,</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">7</i><span face="" style="font-size: 12pt; line-height: 150%;">, 3576), the Friedel-Cafts reaction
(</span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.</i><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2013</b><span face="" style="font-size: 12pt; line-height: 150%;">,</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">3</i><span face="" style="font-size: 12pt; line-height: 150%;">, 7520),</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><span face="" style="font-size: 12pt; line-height: 150%;">[3+2]</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;">
</span><span face="" style="font-size: 12pt; line-height: 150%;">cycloaddition</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><span face="" style="font-size: 12pt; line-height: 150%;">reactions (</span><i style="font-size: 12pt; line-height: 150%;">Tetrahedron</i><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2014</b><span face="" style="font-size: 12pt; line-height: 150%;">,</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">70</i><span face="" style="font-size: 12pt; line-height: 150%;">,1267; </span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.</i><span face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2015</b><span face="" style="font-size: 12pt; line-height: 150%;">,
5, 58464), the Povarov reaction (</span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.</i><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2014</b><span face="" style="font-size: 12pt; line-height: 150%;">,</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">4</i><span face="" style="font-size: 12pt; line-height: 150%;">, 25268), the ene reaction (</span><i style="font-size: 12pt; line-height: 150%;">Org.
Biomol. Chem.</i><span face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2014,</b><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">12</i><span face="" style="font-size: 12pt; line-height: 150%;">,
7581), and recently, the ketene-imine Staudinger reaction (</span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.</i><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2014</b><span face="" style="font-size: 12pt; line-height: 150%;">,</span><span class="apple-converted-space" face="" style="font-size: 12pt; line-height: 150%;"> </span><i style="font-size: 12pt; line-height: 150%;">4</i><span face="" style="font-size: 12pt; line-height: 150%;">, 58559, </span><i style="font-size: 12pt; line-height: 150%;">RSC Adv.</i><span face="" style="font-size: 12pt; line-height: 150%;"> </span><b style="font-size: 12pt; line-height: 150%;">2015</b><span face="" style="font-size: 12pt; line-height: 150%;">,
</span><i style="font-size: 12pt; line-height: 150%;">5</i><span face="" style="font-size: 12pt; line-height: 150%;">, 37119), have been performed using the proposed </span><span face="" style="color: blue; font-size: 12pt; line-height: 150%;"><b>MEDT</b></span><span face="" style="font-size: 12pt; line-height: 150%;">.</span></span><br />
<span face="" style="font-size: 12pt; line-height: 150%;"><br /></span>
<span face="" style="font-size: 12pt; line-height: 150%;"><b style="font-family: arial, helvetica, sans-serif; font-size: medium; text-align: center;">______________________________________________________________________</b></span><br />
<span face="" style="font-size: large; line-height: 150%;"><b style="font-family: arial, helvetica, sans-serif; text-align: center;"><br /></b></span>
<br />
<div class="MDPI12title">
</div>
<div style="text-align: center;">
<span style="font-size: large;"><b><font face="arial">Molecular
Electron Density Theory: </font></b></span></div>
<font face="arial"><span lang=""></span><br />
</font><div style="text-align: center;">
<span lang=""><span style="font-size: large;"><b><font face="arial">A Modern View of Reactivity in Organic Chemistry</font></b></span></span></div>
<font face="arial"><span lang="">
</span>
<br />
</font><div style="text-align: center;">
<span lang=""><b><span lang="" style="mso-ansi-language: EN-GB;"><font face="arial">Luis R. Domingo</font></span></b></span></div>
<font face="arial"><span lang="">
</span>
<br />
</font><div align="center" class="MsoNormal" style="text-align: center;">
<font face="arial"><a href="http://www.mdpi.com/1420-3049/21/10/1319/pdf"><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;">Molecules</span></i><b><span lang="" style="mso-ansi-language: EN-GB;"> 2016</span></b></a><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;"><a href="http://www.mdpi.com/1420-3049/21/10/1319/pdf">, <i>21</i>, 1319</a></span></font></div>
<div align="center" class="MsoNormal" style="text-align: center;">
<font face="arial"><br /></font></div>
<div align="center" class="MsoNormal" style="text-align: center;">
<b><span lang="" style="mso-ansi-language: EN-GB;"><font face="arial">Abstract</font></span></b><span lang="" style="font-family: arial; mso-ansi-language: EN-GB;"><o:p></o:p></span></div>
<div class="MsoNormal">
<span style="font-family: arial;">A new theory for the study of
the reactivity in Organic Chemistry, named Molecular Electron Density Theory
(MEDT), is proposed herein. MEDT is based on the idea that while the electron
density distribution at the ground state is responsible for physical and
chemical molecular properties, as proposed by the Density Functional Theory
(DFT), the capability for changes in electron density is responsible for
molecular reactivity.</span><i style="font-family: arial;"> </i><span style="font-family: arial;">Within MEDT, the reactivity in Organic Chemistry
is studied through a rigorous quantum chemical analysis of the changes of the
electron density as well as the energies associated with these changes along
the reaction path in order to understand experimental outcomes. Studies
performed using MEDT allow establishing a modern rationalisation and to gain
insight into molecular mechanisms and reactivity in Organic Chemistry</span></div>
<div class="MsoNormal">
<span lang="" style="font-family: arial; mso-ansi-language: EN-GB;"><br /></span></div>
<div class="separator" style="clear: both; text-align: center;">
<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEh4oc5j2vnj9bOjyM6Bk8ZK6_MkZUWQFd_YkRLi43vnopnhcnV5rMe3OMKH3b2l5ax7NxU4lOgtxr1ia78ilJi3LLG7J5Eie0GOCajHAadh9TMIQnd74ptN6gRl-NoDk-v2WhuAVrDyru4/s1600/GA.JPG" style="margin-left: 1em; margin-right: 1em;"><img border="0" height="212" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEh4oc5j2vnj9bOjyM6Bk8ZK6_MkZUWQFd_YkRLi43vnopnhcnV5rMe3OMKH3b2l5ax7NxU4lOgtxr1ia78ilJi3LLG7J5Eie0GOCajHAadh9TMIQnd74ptN6gRl-NoDk-v2WhuAVrDyru4/s400/GA.JPG" width="400" /></a></div>
<div class="MsoNormal">
<span lang="" style="font-family: arial; mso-ansi-language: EN-GB;"><br /></span></div>
<div class="MsoNormal">
<span lang="" style="font-family: arial; mso-ansi-language: EN-GB;"><br /></span></div>
<span face="" style="font-size: 12pt; line-height: 150%;"><b style="font-family: arial, helvetica, sans-serif; font-size: medium; text-align: center;">______________________________________________________________________</b></span></div>
</div>
<div class="MsoNormal" style="line-height: 150%; margin-bottom: 0.0001pt;">
<div style="text-align: center;">
<b><span face="" style="font-size: 16pt; line-height: 22.8267px;"><span style="color: blue;"><br /></span></span></b>
<b><span face="" style="font-size: 16pt; line-height: 22.8267px;"><span style="color: blue;">Publications based on MEDT</span></span></b></div>
<br /></div>
</div>
<div class="MsoNormal">
<div style="line-height: 150%;">
<div style="background-color: white; line-height: 150%;">
<span style="font-family: arial;"><span face=""><span style="line-height: 24px;"><b>1.</b> Understanding the high reactivity of carbonyl compounds towards nucleophilic carbenoid intermediates generated from carbene isocyanides. </span><i>RSC Adv.</i><span face=""> </span><b>2015</b><span face="">, </span><i>5</i><span face="">, 84797-84809.</span></span><span face=""><span face=""><br /></span></span></span></div>
<div style="background-color: white; line-height: 150%;">
<span style="font-family: arial;"><span face=""><span style="line-height: 24px;"><b>2.</b> A new model for C-C bond formation processes derived from the <span style="color: blue;">Molecular Electron-Density Theory</span> in the study of the mechanism of [3+2] cycloaddition reactions of carbenoid nitrile ylides with electron-deficient ethylenes. </span><span style="line-height: 150%;"><span style="line-height: 24px;"><i>Tetrahedron</i> </span></span><span style="line-height: 150%;"><b>2016</b>,</span><i style="line-height: 150%;"><span face="">7</span></i><span style="line-height: 150%;"><i>2</i>, 1524-1532.</span></span><span face=""><span style="line-height: 150%;"><br /></span></span></span></div>
<div style="background-color: white; line-height: 150%;">
<span style="font-family: arial;"><span face=""><span style="line-height: 24px;"><b>3. </b>Understanding the carbenoid-type reactivity of nitrile ylides in [3+2] cycloaddition reactions towards electron-deficient ethylenes. A <span style="color: blue;">molecular electron density theor</span><span style="color: blue;">y</span> study. </span><span style="line-height: 150%;"><i>Theor. Chem. Acc.</i> <b>2016</b>, <i>135</i>, 160.</span></span><span face=""><span style="line-height: 150%;"><br /></span></span></span></div>
<div style="background-color: white;">
<span style="font-family: arial;"><span face="" style="line-height: 150%;"><span style="line-height: 150%;"><b>4.</b></span></span><span face=""><span style="line-height: 24px;"> <b>Review:</b> </span></span><span face="" style="line-height: 24px;">Applications of the Conceptual Density Functional Theory Indices to </span></span></div>
<div style="background-color: white;">
<span style="font-family: arial;"><span face=""><span style="line-height: 24px;">Organic Chemistry Reactivity. <i>Molecules</i> <b>2016</b>, <i>21</i>, 748. </span></span><a href="http://www.mdpi.com/1420-3049/21/6/748/pdf" style="line-height: normal; text-align: center;"><span style="line-height: normal; text-align: center;"><span style="line-height: 18px;">Download</span></span><span style="line-height: normal; text-align: center;"><span style="line-height: 13.5pt;"> the Review</span><span style="line-height: 13.5pt;"> </span></span></a>.</span></div>
<div style="background-color: white;">
<span style="font-family: arial;"><span face=""><b>5.</b> An <span style="color: blue;">MEDT</span> study of the carbenoid-type [3+2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones. <i>Org. Biomol. Chem. </i><b>2016</b>,</span><span face=""><span face=""> </span>14, 10427 - 10436.</span></span></div><div style="background-color: white;"><span style="font-family: arial;">
<span face=""><b>6.</b> Electrophilic activation of CO2 in cycloaddition reactions towards a nucleophilic carbenoid intermediate: new defying insights from the <span style="color: blue;">Molecular Electron Density Theory</span>. <i>Theor. Chem. Acc. </i><b>2017</b></span><span face=""><span face="">, </span><span lang="">136:1</span></span><span face="">.</span></span></div><div style="background-color: white;"><span style="font-family: arial;">
<span face=""><b>7.</b> </span><span lang=""><span face="">A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the <st1:citation w:st="on">[3+2]</st1:citation> Cycloaddition Reaction of Nitrones with Ketenes. <i>Org. Biomol. Chem.</i> <b>2017</b>, </span></span><span style="font-size: 12pt;">15, 1618–1627.</span></span></div><div style="background-color: white;"><span style="font-family: arial;">
<span face=""><b>8.</b> </span><span face=""><span style="text-align: center;"><span lang="" style="line-height: 150%;">How does the Global Electron Density
Transfer Diminish Activation Energies in Polar Cycloaddition Reactions? A<span style="color: blue;">
Molecular Electron Density Theory </span>Study.</span></span> </span><span face=""><i>Tetrahedron </i><b>2017</b>, </span><span style="font-size: 12pt;">73,
1718-1724 </span><span face="">.</span></span></div><div style="background-color: white;"><span style="font-family: arial;">
<span face=""><b>9.</b> </span><span face="">Understanding the domino reactions between 1-diazopropan-2-one and 1,1-dinitroethylene. A <span style="color: blue;">molecular electron density theory</span> study of the [3+2] cycloaddition reactions of diazoalkanes with electron-deficient ethylenes. <i>RSC Adv. </i><b>2017</b>, </span><span style="font-size: 12pt;">7, 15586–15595.</span></span></div><div style="background-color: white;"><span style="font-family: arial;">
<span><b>10.</b> Steric interactions controlling the syn diastereofacial selectivity in the [3+2] cycloaddition reaction between acetonitrile axide and 7-oxanorborn-5-en-2-ones. A <span style="color: blue;">Molecular Electron Density Theory study</span>. </span><span>J. Phys. Org. Chem. (2017).</span></span></div>
<div>
<span style="font-family: arial;"><span face=""><b style="background-color: white;">11.</b><span style="background-color: white;"> A</span><span style="background-color: white;"><span style="color: blue;"> Molecular Electron Density Theory Study </span></span><span style="background-color: white;">of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions. Molecules <b>2017</b>, <i>22</i>, 750.</span></span><span face=""><span style="background-color: white;"><br /></span></span>
<span face=""><span style="background-color: white;"><span face=""><b>12.</b></span><span face=""> </span></span></span><span face="">A <span style="color: blue;">Molecular Electron Density
Theory Study</span> of the [3+2] Cycloaddition Reaction of Nitrones with Strained
Allene</span><span style="color: blue;"><span face="">.</span><span style="font-size: 12px;"> </span></span><i style="background-color: white;">RSC Adv. </i><b style="background-color: white;">2017</b><span face="" style="background-color: white; line-height: 17.12px; text-align: center;">,<i> </i></span><i style="background-color: white; text-align: center;">7</i><span face="" style="background-color: white; text-align: center;">, 26879-26887</span><span face="" style="background-color: white;">.</span><br />
</span><div style="background-color: white; text-align: start;">
<div style="text-align: start;">
<span style="font-family: arial;"><span face="" lang=""><b>13.</b> Steric interactions controlling the syn diastereofacial selectivity in the [3+2] cycloaddition reaction between acetonitrile axide and 7-oxanorborn-5-en-2-ones. A <span style="color: blue;">Molecular Electron Density Theory </span>study.<i> </i></span><span face="" lang=""><i>J. Phys. Org. Chem.</i> </span><span face=""><b>2017</b></span><span face="" lang="">.</span></span></div>
</div>
<div style="background-color: white; text-align: start;">
<span style="font-family: arial;"><span face=""><b>14.</b> Understanding the Reactivity and Regioselectivity of [3+2] Cycloaddition Reactions between Substituted Nitrile Oxides and Methyl Acrylate. A<span style="color: blue;"> Molecular Electron Density Theory </span>Study. </span><span face=""><i>Int. J. Quantum Chem.</i> <b>2017</b>.</span><span face=""><br /></span>
<span face=""><b>15.</b><span face=""> A </span><span face="" style="color: blue;">Molecular Electron Density Theory</span><span face=""> study of [3+2] cycloaddition reactions of chiral azomethine ylides with ß-nitrostyrene. </span><i>Theor. Chem. Acc. </i><b>2017</b><span face="">,</span><b><span face=""> </span></b></span><span face="">136:104</span><span face="">.</span><span face=""><br /></span>
<span face=""><b>16.</b> </span><span face="">Understanding the Intramolecular Diels-Alder Reactions of N-Susbtituted N-allyl-furfurylamines. An <span style="color: blue;">MEDT</span> Study. </span><span face=""><span face=""><i>ChemistrySelect </i></span><b>2017</b><span face="">, 2, 9736.</span></span><span face=""><br /></span>
<span face=""><b>17.</b> </span><span face=""><span face="">Understanding the mechanism of the decomposition
reaction of nitroethyl benzoate through the </span><span face="" style="color: blue;">Molecular Electron Density Theory.</span><span face=""> <i>Theor. Chem. Acc.</i> </span><b><span face="">20</span><span face="">17</span></b><span face="">, </span></span><span face="" lang="">136:129.</span><span lang=""> </span><br />
<span face=""><b>18.</b> A <span style="color: blue;">Molecular Electron Density Theory</span> study of the chemo- and regioselective [3+2] cycloaddition reactions between trifluoroacetonitrile N-oxide and thioketones</span><br />
<span face=""><span face="">Chemical Physics <b>2018</b>, </span><i>501</i>, 128-137.</span><span face=""><br /></span>
<span face=""><b>19.</b> Experimental and Theoretical <span style="color: blue;">MEDT</span> Study of the Thermal [3+2] Cycloaddition Reactions of Aryl Azides with Alkyne Derivatives. </span><span face=""><i>ChemistrySelect</i><span face=""> </span><span face=""><b>2018</b>, </span></span><span face=""><i>3</i>, 1215– 1223</span><span style="font-size: 9pt;"><span face="">.</span></span><span face=""><br /></span>
<span face=""><b>20.</b> The Mysticism of Pericyclic Reactions. A Contemporary Rationalisation of Organic Reactivity Based on the Electron Density Analysis. </span><span face=""><i><span face="">Eur. J. Org. Chem</span><span face="">.</span></i><span face=""> </span></span><span face=""><b>20</b></span><span face=""><b>18</b>, </span><span face="">1107–1120</span><span face="">.</span><span face=""><br /></span>
<span face=""><b>21.</b> A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the Reactivity and Selectivities in [3+2] Cycloaddition Reactions of C,N-Dialkyl Nitrones with Ethylene Derivatives. </span><span face=""><i>J. Org. Chem.</i><span face=""> <b>2018</b>,</span><span face=""> </span></span><span face=""><i>83</i>, 2182−2197</span><span style="font-size: 9pt;"><span face="">.</span></span><span face=""><br /></span>
<span face=""><span face=""><b>22.</b> </span><span face="">A <span style="color: blue;">Molecular Electron Density Theory</span> study of the [3+2] cycloaddition reaction between an azomethine imine and electron deficient ethylenes. </span><span face=""><i>J. Phys. Org. Chem</i></span><span face=""><span face=""><i>. </i><b>2017</b>, </span>31:e3830</span><span face="">.</span></span><span face=""><span face=""><br /></span>
<span face=""><b>23.</b> </span><span face="" style="text-align: start;"> </span><span face="" style="text-align: start;"><span style="color: blue;">Molecular Electron Density Theory</span> Study of Fused Regioselectivity in the Intramolecular [3+2] Cycloaddition Reaction of Nitrones. <i>ChemistrySelect</i> <b>2018</b>, </span>3, 5412–5420.</span><span face="" style="text-align: start;"><b><br /></b></span>
<span face="" style="text-align: start;"><b>24.</b> A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the Role of the Copper-Metallation of Azomethine Ylides in [3+2] Cycloaddition Reactions. <i>J.</i></span><span face="" style="text-align: start;"><i> Org. Chem.</i> <b>2018</b>,</span><span lang=""><span face=""> <i>83</i>, 10959-</span></span><span face="">10973.</span><span face="" style="text-align: start;"><br /></span>
<span face=""><span face="" style="text-align: start;"><b>25.</b> </span>A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the Competitiveness of Polar Diels-Alder and Polar Alder Ene Reactions. <i>Molecules </i><b>2018, </b></span><span face=""><span lang=""><i>23</i></span><span lang="">, 1913</span></span><span face="">.</span><span face=""><span face="" style="text-align: start;"><span face=""><br /></span></span></span>
<span face=""><span face="" style="text-align: start;"><span face=""><b>26.</b> A <span style="color: blue;">Molecular Electron Density Theory </span>Study of the Chemoselectivity, Regioselectivity and Diastereofacial Selectivity in the Synthesis of an Anti-Cancer Spiro-Isoxazoline derived from α-Santonin. </span><span face=""><i>Molecules</i></span><span face=""><i> </i><b>2019</b>, </span></span><span face="" style="text-align: start;"><span lang=""><i>24</i>, </span><span lang="">832.</span></span></span><span face=""><span face="" style="text-align: start;"><span lang=""><br /></span></span></span>
<span face=""><b>27</b>. Understanding the Mechanism of Nitrobenzene Nitration with Nitronium Ion. <span style="color: blue;">A Molecular Electron Density Theory Study</span>. </span><span face=""><i>ChemistrySelect</i> <b>2019</b>, <i>4</i>, 13313–13319</span><span face=""><br /></span>
<span face=""><b>28</b>. A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the Enhanced Reactivity of Aza Aromatic Compounds Participating in Diels-Alder Reactions. </span><span face=""><i>Org. Biomol. Chem.</i> <b>2020</b>, <i>18</i>, 292 –304</span><span face=""><br /></span>
<span face=""><b>29.</b> A <span style="color: blue;">molecular electron density theory</span> study of the Grignard reagent-mediated regioselective direct synthesis of 1,5-disubstituted-1,2,3-triazoles. </span><span face=""><i>J. Phys. Org. Chem. </i><b>2020</b>, e4062</span><span face=""><br /></span>
<span face=""><b>30.</b> Unveiling the Different Chemical Reactivity of Diphenyl Nitrilimine and Phenyl Nitrile Oxide in [3+2] Cycloaddition Reactions with (R)-Carvone through the <span style="color: blue;">Molecular Electron Density Theory</span>. </span><span face=""><i>Molecules </i><b>2020</b>, <i>25</i>, 1085.</span><span face=""><br /></span>
<span face=""><b>31</b>. A <span style="color: blue;">Molecular Electron Density Theory</span> Study of the Reactivity of Tetrazines in Aza-Diels-Alder Reactions. <i>RSC Adv. </i><b>2020</b>, <i>10</i>, 15394.</span><br />
<span face=""><b>32</b>. A <span style="color: blue;">molecular electron density theory</span> study on an oxa-Diels-Alder reaction: exploration of different impacts of AlCl3 as a Lewis acid catalyst. <i>ChemistrySelect</i> <b>2020</b>, <i>5</i>, 5341.<br /></span></span>
<font face="arial"><span><b>33</b>. </span><span><font face="">Unveiling the Lewis Acid Catalysed Diels–Alder Reactions Through the </font><span style="color: blue;">Molecular Electron Density Theory</span><font face="">. </font><i><font face="">Molecules</font> </i></span><span style="background-color: transparent;"><b>2020</b>, <i>25</i>, 2535</span>.</font></div><div style="background-color: white; text-align: start;"><font face="arial"><b>34. </b><span style="background-color: transparent;">Unveiling
the High Reactivity of Strained Dibenzocyclooctyne in [3+2] Cycloaddition
Reactions with Diazoalkanes through the <font color="#2b00fe">Molecular Electron Density Theory</font>. </span><span style="background-color: transparent;"><i>J.
Phys. Org. Chem.</i> <b>2020,</b> e4100.</span></font></div><div style="background-color: white; text-align: start;"><font face="arial" style="background-color: transparent; text-align: left;"><b>35.</b> A <font color="#2b00fe">Molecular Electron Density Theory</font> Study of the [3+2] Cycloaddition Reaction of 1,4-Diphosphorinium-3-olates with Methyl Acrylate and Methyl Methacrylate. <i>Theor. Chem. A</i></font><font face="arial" style="background-color: transparent; text-align: left;"><i>cc.</i> <span lang=""><b>2020</b>, <i>139</i>:124</span>.</font></div><div style="background-color: white; text-align: start;"><font style="background-color: transparent; text-align: left;"><div style="font-family: arial; text-align: start;"><b>36.</b> Unravelling the Strain-Promoted [3+2] Cycloaddition Reactions of Phenyl Azide with Cycloalkynes from the <font color="#2b00fe">Molecular Electron Density Theory</font> Perspective. <i>New J. Chem.</i> <b>2020,</b> <span style="background-color: transparent;"><i>44</i>, 13633</span></div><div style="font-family: arial; text-align: start;"><b>37.</b> <span style="background-color: transparent; text-align: justify;">Unveiling the High Reactivity of Benzyne in the Formal [3+2] Cycloaddition Reactions towards Thioamides through the <font color="#2b00fe">Molecular Electron Density Theory</font>. </span><span style="text-align: justify;"><i>Tetrahedron </i><b>2020</b>, <i>76</i>, 131458.</span></div><div style="font-family: arial; text-align: start;"><span style="text-align: justify;"><b>38.</b> </span><span style="text-align: justify;">The Lithium Cation Catalysed Benzene Diels-Alder reaction. Insights on the Molecular Mechanism within the <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. </span><span style="text-align: justify;"><i>J. Org. Chem.</i> <b>2020</b>, <i>85</i>, 13121−13132.</span></div><div style="font-family: arial; text-align: start;"><span style="text-align: justify;"><b>39.</b> </span><span style="background-color: transparent;">Unveiling the Reactivity of Cyclic Azomethine Ylides in [3+2] Cycloaddition Reactions within the <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. <i>Eur. J. Org. Chem. </i><b>2020, </b></span><span style="background-color: transparent;">5938–5948</span><span style="background-color: transparent;">.</span></div><div style="font-family: arial; text-align: start;"><span style="background-color: transparent;"><b>40.</b> </span>A<span style="color: #2b00fe;"> Molecular Electron Density Theory</span> (MEDT) study of the role of halogens (X2= F2, Cl2, Br2 and I2) on the aza-Michael-addition reactions. <i>New J. Chem.</i> <span lang="es"><b>2020</b>, <i>44</i>, 19002-19012</span>.</div><div style="font-family: arial; text-align: start;"><b>41.</b> Understanding the Origin of the Regioselectivity in Non-polar [3+2] Cycloaddition Reactions through the <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. Organics <b>2020</b>, <i>1</i>, 19-35.</div><div style="font-family: arial; text-align: start;"><b>42.</b> <span style="background-color: transparent;">Unveiling the Unexpected Reactivity of Electrophilic Diazoalkanes in [3+2] Cycloaddition Reactions within <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. </span><i>Chemistry </i><b>2021, </b><span style="background-color: transparent; font-family: "Times New Roman", serif; font-size: 12px;"> </span><span style="background-color: transparent; font-family: "Times New Roman", serif; font-size: 12px;">3, 74–93</span><span style="background-color: transparent;">. </span></div><div style="text-align: start;"><span style="background-color: transparent;"><span style="font-family: arial;"><b>43.</b> </span></span><span style="font-family: arial;"><span lang="EN-US" style="background-color: transparent;">Understanding the different reactivity of (Z)- and (E)-</span><span lang="EN-US" style="background-color: transparent;">b</span><span lang="EN-US" style="background-color: transparent;">-nitrostyrenes in [3+2]
cycloaddition reactions. An <span style="color: #2b00fe;">MEDT</span> study. </span><span style="background-color: transparent;"><i>RSC Adv.</i> <b>2021</b>, <i>11</i>, 9698–9708.</span></span></div><div style="text-align: start;"><span style="font-family: arial;"><b>44. </b>Unveiling the Ionic
Diels-Alder Reactions within the <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. <i>Molecules</i> <b>2021</b>, <i>26</i>,
3638.</span></div><div style="text-align: start;"><span style="font-family: arial;"><b>45.</b> Unveiling the
Regioselectivity in Electrophilic Aromatic Substitution Reactions of
Deactivated Benzenes through <span style="color: #2b00fe;">Molecular Electron Density Theory</span>. <i>New J. Chem.</i> <b>2021</b>,
<i>45</i>, 13626–13638.</span></div><div style="text-align: start;"><span style="font-family: arial;"><b>46.</b> Unveiling the
Intramolecular Ionic Diels-Alder Reactions within the <span style="color: #2b00fe;">Molecular Electron
Density Theory</span>. <span lang="ES-TRAD"><i>Chemistry </i></span><span lang="ES-TRAD"><b>2021</b></span><span lang="ES-TRAD">, <i>3</i>, 834–853.</span></span></div><div style="text-align: start;"><span style="font-family: arial;"><span lang="ES-TRAD"><b>47.</b> </span>Understanding
the Participation of Fluorinated Azomethine Ylides in Carbenoid-type [3+2] Cycloaddition
Reactions with Ynal Systems: A <span style="color: #2b00fe;">Molecular Electron Density Theory </span>Study. <i>J.
Org. Chem.</i> <b>2021</b>, <i>86</i>, 12644−12653.</span></div><div style="text-align: start;"><span style="font-family: arial;"><b>48.</b> On
the Catalytic Effects of the Thiazolium Salt in the Oxa-Diel-Alder Reaction
between Benzaldehyde and Danishefsky’s Diene: A <span style="color: #2b00fe;">Molecular Electron Density
Theory</span> Study. <span lang="ES-TRAD"><i>Org. Biomol. Chem.</i> </span><span lang="es"><b>20</b></span><span lang="EN-US"><b>21</b></span></span><span style="background-color: transparent; font-family: "Times New Roman", serif; font-size: 9pt;">,</span><span style="background-color: transparent;"><span style="font-family: arial;"> <i>19</i>, 9306-9317.</span></span></div><div style="text-align: start;"><span style="font-family: arial;"><span><span lang="es"><b>49.</b> </span></span>A <span style="color: #2b00fe;">Molecular Electron Density Theory</span> Study of the Higher–Order Cycloaddition Reactions of Tropone with Electron-rich Ethylene. The Role of the Lewis Acid Catalyst in the Mechanism and Pseudocyclic Selectivity.<i> New J. Chem. </i><b>2021</b>, <i>46</i>, 294–308.</span></div></font><div><b style="font-family: arial;">50. </b><span style="font-family: arial;">A <span style="color: #2b00fe;">Molecular Electron Density Theory</span> Study of the Lewis Acid Catalyzed [3+2] Cycloaddition Reactions of Nitrones with Nucleophilic Ethylenes. <i>Eur. J. Org. Chem. </i>(<b>2021</b>)</span></div></div>
</div>
<div style="background-color: white; text-align: center;">
</div>
<div style="background-color: white; line-height: 150%;">
<span face="" style="font-size: 12pt; line-height: 24px;"><b style="font-family: arial, helvetica, sans-serif; font-size: medium; text-align: center;">______________________________________________________________________</b></span><br />
<div>
<span face="" style="font-size: 12pt; line-height: 24px;"><b style="font-family: arial, helvetica, sans-serif; font-size: medium; text-align: center;"><br /></b></span></div>
</div>
</div>
</div>
<div class="MsoNormal" style="background-color: white; line-height: 150%;">
<div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<b><span face="" style="font-size: 16pt; line-height: 107%;"><span style="color: blue;">MEDT versus FMO theory</span><span style="color: red;"><o:p></o:p></span></span></b></div>
<div class="MsoNormal" style="line-height: 150%; margin-bottom: 0.0001pt;">
<br /></div>
<div class="MsoNormal" style="line-height: 150%; margin-bottom: 0.0001pt;">
<div class="MsoNormal" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial;">
<span lang="" style="font-family: arial;">In</span><span class="apple-converted-space"><span lang="" style="font-family: arial; font-size: 10.5pt;"> </span></span><span lang="" style="font-family: arial;">1926,<span class="apple-converted-space"> </span>Schrödinger published the so-called
Schrödinger equation, which describes the electronic structure for a system
formed by a set of nuclei and the corresponding electrons. Due to the
complexity of the mathematical resolution of the Schrödinger equation for
organic molecules containing a few atoms, a series of physical/ mathematical
approaches were developed. One of them was the Molecular Orbital theory (MOT),
in which the wavefunction<span class="apple-converted-space"> </span></span><span style="font-family: symbol;">Y</span><span class="apple-converted-space"><span style="font-family: arial;"> </span></span><span lang="" style="font-family: arial;">is obtained as the sum of a series
of simpler wavefunctions<span class="apple-converted-space"> </span></span><span style="font-family: symbol;">Y</span><sub><span lang="" style="font-family: arial;">i</span></sub><span class="apple-converted-space"><span lang="" style="font-family: arial;"> </span></span><span lang="" style="font-family: arial;">named<span class="apple-converted-space"> </span>molecular orbitals (MOs). The simplest
approach to the MOT was the Hückel molecular orbital theory (HMOT) established
in <st1:metricconverter productid="1930, in" w:st="on">1930, in</st1:metricconverter>
which only valence atomic orbitals (AOs) are used to build MOs. In the simplest
HMOT, only p<sub>z</sub><span class="apple-converted-space"> </span>AOs were used
in the study of planar unsaturated molecules. This very simple approach, which
is widely used in organic chemistry nowadays, was employed in the 50s of the
last century to establish important organic reactivity models such as the
pericyclic mechanism for cycloaddition reactions, as well as the frontier
molecular orbital (FMO) theory for the study of the reactivity in organic
chemistry. Today, the HMOT is too simple to describe the structure and
reactivity of organic molecules. On the other hand, the total electron density
obtained from MO calculations comes from the sum of the occupied MOs, the individual
analysis of any MO has no physical significance.</span><span lang="" style="font-family: arial; font-size: 5pt;"><o:p></o:p></span></div>
<div class="MsoNormal" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial;">
<span lang="" style="font-family: arial;">In the
last decade of the last century, first Bader and later Becke and Edgecombe
established quantum tools allowing the topological analysis of the electron
density,<span class="apple-converted-space"> </span>i.e.<i> </i>Atoms in Molecules (AIM) and Electron Localisation
Function (ELF). While AIM<span class="apple-converted-space"> </span>enables a
partition of the electron density within the molecular space into basins
associated with atoms, ELF constitutes a useful relative measure of the
electron pair localisation characterising the corresponding electron density.<span class="apple-converted-space"> </span>Silvi and Savin presented the ELF in a very
chemical fashion, using their topological analysis as an appealing model of
chemical bonding.<o:p></o:p></span></div>
<div class="MsoNormal" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial;">
<span lang="" style="font-family: arial;">From
the beginning of the present century, theoretical organic chemists have had powerful
quantum-chemical tools at their disposal to perform a rigorous analysis of the
changes of electron density along a reaction channel and thus to establish
reactivity in organic chemistry. Numerous works carried out in this century by
recognised scientists have demonstrated the ability of these tools to study reactivity
in organic chemistry.<o:p></o:p></span></div>
<span face="" style="font-size: 12pt; line-height: 150%;"><span style="font-family: arial; line-height: 150%;">Consequently,
from my point of view, the use of the FMO theory to study reactivity in organic
chemistry is completely out of date, necessitating a rigorous analysis of the
changes of electron density along an organic reaction.</span></span></div>
<div style="line-height: 150%;">
<br /></div>
<div style="line-height: 150%;">
<div style="text-align: center;">
<br />
<div style="-webkit-text-stroke-width: 0px; background-color: white; color: black; font-family: "times new roman"; font-size: medium; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: 24px; orphans: auto; text-align: center; text-indent: 0px; text-transform: none; white-space: normal; widows: 1; word-spacing: 0px;">
</div>
<span style="font-family: arial;"><br />
</span><div style="background-color: white; color: black; font-size: medium; font-style: normal; font-variant: normal; letter-spacing: normal; line-height: 24px; text-align: justify; text-indent: 0px; text-transform: none; white-space: normal; word-spacing: 0px;">
<div style="margin: 0px;">
<span face=""><span style="line-height: 24px;"><span style="font-family: arial; text-align: center;"><b>______________________________________________________________________</b></span></span></span></div>
</div>
</div>
</div>
<div style="line-height: 150%; text-align: center;">
<span style="font-family: arial;"><span face="" style="color: blue; font-size: large;"><br /></span>
<span face="" style="font-size: large;"> <b>Review</b></span></span></div>
<div style="line-height: 150%; text-align: center;">
<span style="font-family: arial;"><b><br /></b></span></div>
<div style="line-height: 150%; text-align: center;">
<span style="font-family: arial; font-size: medium; line-height: 24px;"><b>Applications of the Conceptual Density Functional Theory Indices to </b></span></div>
<div style="line-height: 150%; text-align: center;">
<span face=""><span style="font-family: arial; font-size: medium; line-height: 24px;"><b>Organic Chemistry Reactivity.</b></span></span></div>
<div style="line-height: 150%; text-align: center;">
<span face=""><span style="font-family: arial; line-height: 24px;"><b><br /></b></span></span></div>
<div style="line-height: 150%; text-align: center;">
<span face=""><span style="line-height: 24px;"><span style="font-family: arial;">Luis R. Domingo, Mar Ríos-Gutiérrez and Patricia Pérez</span></span></span></div>
<div style="line-height: 150%; text-align: center;">
<span face=""><span style="font-family: arial; line-height: 24px;"><i>Molecules</i>, <b>2016</b>, <i>21</i>, 748.</span></span></div>
<div style="line-height: 150%; text-align: center;">
<span style="font-family: arial;"><span face="" style="line-height: 150%;"><br /></span>
<span face="" style="line-height: 150%;"><a href="http://www.mdpi.com/1420-3049/21/6/748/pdf" style="line-height: normal;"><span style="line-height: normal;"><span style="line-height: 18px;">Download</span></span><span style="line-height: normal;"><span style="line-height: 13.5pt;"> the Review</span><span style="line-height: 13.5pt;"> </span></span></a></span></span></div>
<div style="line-height: 150%; text-align: center;">
<span style="font-family: arial; line-height: 150%;"><br /></span></div>
<div style="line-height: 150%; text-align: justify;"><p class="MsoNormal" style="line-height: 150%; margin-bottom: 0.0001pt;"><span face="Arial, sans-serif" lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-size: 12pt; line-height: 150%;">Theoretical reactivity indices based on the conceptual Density
Functional Theory (DFT) have become a powerful tool for the semiquantitative
study of organic reactivity. A large number of reactivity indices have
been proposed in the literature. Herein, global quantities like the electronic chemical
potential </span><i><span lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-family: Symbol; font-size: 12pt; line-height: 150%;">m</span></i><span face="Arial, sans-serif" lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-size: 12pt; line-height: 150%;">, the electrophilicity </span><i><span lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-family: Symbol; font-size: 12pt; line-height: 150%;">w</span></i><span face="Arial, sans-serif" lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-size: 12pt; line-height: 150%;">, </span><span face="Arial, sans-serif" lang="EN-US" style="background-attachment: initial; background-clip: initial; background-image: initial; background-origin: initial; background-position: initial; background-repeat: initial; background-size: initial; font-size: 12pt; line-height: 150%;">and the
nucleophilicity <i>N</i> indices, and local condensed indices
like the electrophilic and nucleophilic <i>P(r) </i>Parr functions, as the most relevant indices
for the study of organic reactivity, are discussed.</span><span lang="EN-US" style="font-size: 12pt; line-height: 150%; mso-ansi-language: EN-US;"><o:p></o:p></span></p><span style="font-family: arial;">
<span face=""><br /></span>
<br />
</span><div class="MsoBodyTextIndent" style="line-height: 150%; text-indent: 0cm;">
<span lang="" style="font-family: arial; mso-ansi-language: EN-GB;"><b>Content</b><o:p></o:p></span></div>
<div class="MsoBodyTextIndent" style="line-height: 150%; tab-stops: -32.55pt; text-indent: 0cm;">
<div class="MsoBodyTextIndent" style="line-height: normal; tab-stops: -32.55pt; text-indent: 0cm;">
<span style="font-family: arial;"><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;">1. Electronic
Chemical Potential </span></i><i><span lang="" style="mso-ansi-language: EN-GB; mso-ascii-font-family: Arial; mso-bidi-font-family: Arial; mso-bidi-font-weight: bold; mso-char-type: symbol; mso-hansi-font-family: Arial; mso-symbol-font-family: Symbol;">m</span></i><i><span lang="" style="mso-ansi-language: EN-GB;"> and Mulliken
Electronegativity </span></i><i><span lang="" style="mso-ansi-language: EN-GB; mso-ascii-font-family: Arial; mso-bidi-font-family: Arial; mso-bidi-font-weight: bold; mso-char-type: symbol; mso-hansi-font-family: Arial; mso-symbol-font-family: Symbol;">c</span></i><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;"><o:p></o:p></span></i></span></div>
<div class="MsoBodyTextIndent" style="line-height: normal; tab-stops: -32.55pt 0cm; text-indent: 0cm;">
<span style="font-family: arial;"><i><span lang="">2. Chemical Hardness </span></i><i><span lang="" style="mso-ascii-font-family: Arial; mso-bidi-font-family: Arial; mso-char-type: symbol; mso-hansi-font-family: Arial; mso-symbol-font-family: Symbol;">h</span></i><i><span lang=""> and Softness S</span></i><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;"><o:p></o:p></span></i></span></div>
<div class="MsoBodyText" style="line-height: normal;">
<i><span lang="" style="font-family: arial;">3. The <st1:city w:st="on"><st1:place w:st="on">Fukui</st1:place></st1:city>
Functions</span></i><i><span lang="" style="font-family: arial;"> f</span></i><i><span lang="" style="font-family: arial;">(r)</span></i><i><span lang="" style="font-family: arial;"><o:p></o:p></span></i></div>
<div class="MsoBodyTextIndent" style="line-height: normal; tab-stops: -32.55pt 0cm; text-indent: 0cm;">
<span style="font-family: arial;"><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;">4. The
Electrophilicity </span></i><i><span lang="">w</span></i><i><span lang="" style="mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;"> Index<o:p></o:p></span></i></span></div>
<div class="MsoNormal" style="break-after: avoid;">
<i><span lang="" style="font-family: arial; position: relative; top: 0pt; vertical-align: baseline;">5. The Nucleophilicity N Index<o:p></o:p></span></i></div>
<div class="NormalTeth" style="line-height: normal; tab-stops: -32.55pt; text-indent: 0cm;">
<span style="font-family: arial;"><i><span lang="">6. Local
Electrophilicity </span></i><i><span lang="">w</span></i><i><sub><span lang="">k</span></sub></i><i><span lang=""> and Nucleophilicity </span></i><i><span lang="">N<sub>k</sub></span></i><i><span lang=""> Indices <o:p></o:p></span></i></span></div>
<div class="NormalTeth" style="line-height: normal; tab-stops: -32.55pt; text-indent: 0cm;">
<i><span lang="" style="font-family: arial; mso-ansi-language: EN-GB;">7. The Parr Functions</span></i><i><span lang="" style="font-family: arial;"> P</span></i><i><span lang="" style="font-family: arial;">(r)</span></i><i><span lang="" style="font-family: arial;"><o:p></o:p></span></i></div>
<div class="MsoBodyText" style="line-height: normal;">
<i><span lang="" style="font-family: arial;">8. The </span></i><i><span lang="" style="font-family: arial; mso-ansi-language: EN-GB; mso-bidi-font-weight: bold;">Local Reactivity Difference
Index R<sub>k</sub></span></i></div>
<div class="MsoNormal">
<i><span lang="" style="font-family: arial; vertical-align: baseline;">9. Electrophilic
and nucleophilic free radicals<span style="font-size: 12pt;"><o:p></o:p></span></span></i></div>
</div>
</div>
<div style="line-height: 150%;">
<span face=""><span style="line-height: 150%;"><b style="text-align: center;">_________________________________________________________________________</b></span></span></div>
<div style="line-height: 150%; text-align: center;">
<br /></div>
<div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<span style="font-family: arial;"><b><span lang="">The first citation to MEDT</span></b><br />
<b><span lang=""><br /></span></b>
<b><span lang="">Understanding the high reactivity of carbonyl compounds towards
nucleophilic carbenoid intermediates generated from carbene isocyanides</span></b><span style="line-height: 150%;"> </span></span></div><div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;"><span style="font-family: arial; line-height: 150%;"><br /></span></div>
<div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<span style="font-family: arial;">M. Ríos-Gutiérrez, L.
R. Domingo, and P Pérez</span></div>
<div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<span style="font-family: arial;"><span><br /></span><span lang=""><span face=""><i>RSC Adv.</i> <b>2015</b>, <i>5</i>, 84797-84809</span></span><br />
<span face=""><span style="background-color: white; line-height: 18px; text-align: start;"><br /></span></span>
<a href="http://pubs.rsc.org/en/content/articlelanding/2015/ra/c5ra15662a#!divAbstract" style="line-height: normal;"><span style="line-height: normal;"><span style="line-height: 18px;">Download</span></span><span style="line-height: normal;"><span style="line-height: 13.5pt;"> the Open </span><span style="line-height: 18px;">Access Article</span><span style="line-height: 13.5pt;"> </span></span></a></span></div>
<div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<br /></div>
<div class="MsoNormal" style="line-height: 150%;">
<span lang="" style="font-family: arial;">The high
nucleophilic character of carbenoid intermediate <i>cis-</i><b>IN </b>together with the
specific approach mode of acetone make the formation of the C-C single bond
with a very low activation free energy, possible. The proposed <b><span style="color: blue;">MEDT</span></b> model allows explaining
the reaction mechanism of these cycloaddition reactions as a <st1:citation w:st="on">[2n+2n]</st1:citation> cycloaddition. This study makes it possible to
reject a recently proposed theoretical study based on the obsolete FMO theory, which
proposes a 1,3-dipolar cycloaddition mechanism for these reactions (</span><i><span lang="" style="font-family: arial; mso-ansi-language: EN-GB;">J. Org. Chem.</span></i><span lang="" style="font-family: arial; mso-ansi-language: EN-GB;">, 2014, <b>79</b>, 10811).</span></div>
<div class="separator" style="clear: both; line-height: 150%; text-align: center;">
<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEjh5dsY9Rj_RpZDhx_wOCj_nZgbUtdnpj8QLQHWSE98ckh3MlUBW-jztB7Xw0LeDHWUHIMzXxM5TFHy0A7A6FVEjLYUHBFigiYNAUjREvkNdTwZ4XEH4JQVyTKxX9TfUIMCnZ0T20I6iZQ/s1600/medt.jpg" style="margin-left: 1em; margin-right: 1em;"><img border="0" height="200" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEjh5dsY9Rj_RpZDhx_wOCj_nZgbUtdnpj8QLQHWSE98ckh3MlUBW-jztB7Xw0LeDHWUHIMzXxM5TFHy0A7A6FVEjLYUHBFigiYNAUjREvkNdTwZ4XEH4JQVyTKxX9TfUIMCnZ0T20I6iZQ/s200/medt.jpg" width="173" /></a></div>
<div style="line-height: 150%; text-align: center;">
<span face=""><span style="line-height: 150%;"><b>_________________________________________________________________________</b></span></span></div>
<div style="line-height: 150%;">
<span face=""><span style="line-height: 150%;"><br /></span></span>
<span face="">Domingo has</span><span face=""> reached the following bibliometric
rates:</span><br />
<span face="">
<br /><b> Publications: 360<br /> Citations: 14.400<br /> Index h: 56</b><br />
<br />
Thanks to those who have contributed to this vast work, and those
who have read and cited the corresponding publications.</span></div>
<div style="line-height: 150%;">
<span face=""><br /></span>
<a href="http://scholar.google.es/citations?user=mqrQU_wAAAAJ&hl=es" style="font-family: georgia, serif; font-size: 16px; line-height: normal; text-align: left;">Access to Citations in Scholar Goggle</a></div>
</div></div><div class="MsoNormal" style="background-color: white; line-height: 150%;"><div style="text-align: center;"><div style="text-align: center;"><br /></div></div></div>
<div style="background-color: white; line-height: 150%;">
<div style="text-align: center;">
<span face=""><b>_________________________________________________________________________</b></span></div>
<div>
<span style="font-family: arial;"><br /></span></div>
</div>
</div>
<div style="background-color: white; line-height: 150%; text-align: center;">
<span style="font-family: arial;">Review article</span></div><div style="background-color: white; line-height: 150%; text-align: center;"><span style="font-family: arial;"><br /></span></div>
<div style="background-color: white; line-height: 150%;">
</div>
<h2 align="center" style="background-color: white; line-height: 15.75pt; margin: 0cm 0cm 0.0001pt; text-align: center;">
<span><span style="font-family: arial; font-size: medium;">A New C-C Bond Formation Model
Based on the Quantum Chemical Topology of Electron Density</span></span></h2><div><span><span style="font-family: arial; font-size: medium;"><br /></span></span></div>
<div style="background-color: white; line-height: 150%; text-align: center;">
<span style="font-family: arial;"><i>Luis R. Domingo</i></span></div>
<div align="center" class="MsoNormal" style="background-color: white; line-height: 13.5pt; text-align: center;">
<span style="font-family: arial;"><br /></span></div>
<div align="center" class="MsoNormal" style="background-color: white; line-height: 13.5pt; text-align: center;">
<i><span style="font-family: arial;"><a href="http://pubs.rsc.org/en/content/articlelanding/2014/ra/c4ra04280h#!divAbstract">RSC Adv.</a></span></i><span style="font-family: arial;"><a href="http://pubs.rsc.org/en/content/articlelanding/2014/ra/c4ra04280h#!divAbstract">, 2014, 4, 32415-32428</a><span style="font-size: 9pt;"><o:p></o:p></span></span></div>
<div align="center" class="MsoNormal" style="background-color: white; text-align: center;">
<span style="font-family: arial;"><span><span style="font-size: 12px; line-height: 18px;"><br /></span></span>
<a href="http://pubs.rsc.org/en/content/articlepdf/2014/ra/c4ra04280h"><span><span style="font-size: 12px; line-height: 18px;">Download</span></span><span><span style="font-size: 9pt; line-height: 13.5pt;"> the Open </span><span style="font-size: 12px; line-height: 18px;">Access</span><span style="font-size: 9pt; line-height: 13.5pt;"> Review</span></span></a></span></div>
<div class="MsoNormal" style="background-color: white; line-height: 13.5pt; text-align: justify;">
<span style="font-family: arial;"><span style="font-size: 9pt; line-height: 13.5pt;"><br /></span>
<span face=""><span style="line-height: 13.5pt;">ELF topological analyses of bonding changes in non-polar, polar and ionic organic reactions involving the </span><span style="line-height: 13.5pt;"> </span><span style="line-height: 13.5pt;">participation of C=C(X) double bonds make it possible to establish a unified model for C-C bond formation. This model is characterised by a C-to-C coupling of two <i>pseudoradical </i>centers (</span></span></span><span style="background-color: transparent;"><span style="font-family: arial;"><i>J. Org. Chem.</i> <b>2011</b>, <i>76</i>, 373) </span></span><span style="font-family: arial; line-height: 13.5pt;"> generated at the most significant atoms of the reacting molecules. The global electron density transfer (GEDT) process that takes place along polar and ionic reactions favours the creation of these pseudoradical centers at the most nucleophilic/electrophilic centers of the reacting molecules, decreasing activation energies. The proposed reactivity model based on the topological analysis of the changes in electron density along a reaction makes it possible to reject the frontier molecular orbital reactivity model based on the analysis of molecular orbitals</span><span style="color: #222222; font-family: arial;">.</span></div>
<div align="right" class="MsoNormal" style="background-color: white; line-height: 13.5pt; text-align: right;">
<span style="font-family: arial;"><br />
</span><div class="separator" style="clear: both; text-align: center;">
<a href="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgDXqlOh1vVsqvUKWite0uTkY_vcTqbTkxeZ1Be6j2HZqnzEPHo4mlhdhaSM5xmnaVSqK27NLt8uOqB7qrdvkU4T4wlZxlVbTwWRagF7GueRk2QgTVpTIhNYpPN5O3dz8hi0A88gXuYJdQ/s1600/enlaces.jpg" style="margin-left: 1em; margin-right: 1em;"><span style="font-family: arial;"><img border="0" height="156" src="https://blogger.googleusercontent.com/img/b/R29vZ2xl/AVvXsEgDXqlOh1vVsqvUKWite0uTkY_vcTqbTkxeZ1Be6j2HZqnzEPHo4mlhdhaSM5xmnaVSqK27NLt8uOqB7qrdvkU4T4wlZxlVbTwWRagF7GueRk2QgTVpTIhNYpPN5O3dz8hi0A88gXuYJdQ/s1600/enlaces.jpg" width="320" /></span></a></div>
<span style="font-family: arial;"><br />
</span><div align="center" class="MsoNormal" style="line-height: 150%; text-align: center;">
<i><span lang="" style="font-family: arial; line-height: 150%;">Pseudodiradical</span></i><span lang="" style="font-family: arial; line-height: 150%;"> structures and GEDT involved in the C-C
single bond formation in non-polar, polar and ionic organic reactions.<o:p style="font-size: 10pt;"></o:p></span></div>
</div>
<div class="red_txt_s4" style="background-color: white; float: left; font-family: arial, helvetica, sans-serif; font-size: 12px; line-height: 18px; text-align: justify; width: 360px;">
<span style="color: #222222; font-family: arial; text-align: start;">.</span></div>
</div>
<div class="MsoNormal" style="background-color: white; text-align: justify;">
<div align="center" style="background-position: initial initial; background-repeat: initial initial; margin: 0cm 0cm 0.0001pt; text-align: center;">
</div>
</div>
</div>
</div>
</div>
luisrdomingohttp://www.blogger.com/profile/00145107227339444002noreply@blogger.com