PUMA publications for /tag/VIA%2015https://puma.ub.uni-stuttgart.de/tag/VIA%2015PUMA RSS feed for /tag/VIA%20152024-03-28T13:48:08+01:00Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzenehttps://puma.ub.uni-stuttgart.de/bibtex/2dd247d6e4f6157daed586230a3310cbf/huebleriachuebleriac2022-06-15T11:26:56+02:0015 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Judith C. Giordan" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/0"><span itemprop="name">J. Giordan</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="John H. Moore" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/1"><span itemprop="name">J. Moore</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="John A. Tossell" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/2"><span itemprop="name">J. Tossell</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/3"><span itemprop="name">W. Kaim</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Journal of the American Chemical Society</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">107 </span></span>(<span itemprop="issueNumber">20</span>):
<span itemprop="pagination">5600--5604</span></em> </span>(<em><span>1985<meta content="1985" itemprop="datePublished"/></span></em>)</span>Wed Jun 15 11:26:56 CEST 2022Journal of the American Chemical Society205600--5604Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzene107198515 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission Electron-transmission spectroscopy was used to det. the energies of low-lying neg.-ion states of MenM (M = N, P, As, n = 3; M = O, S, n = 2) as well as p-(MenM)2C6H4 (M = N, As, n = 3; M = O, S, n = 2). Spectral peaks are obsd., corresponding to electron capture into benzene \textgreek{p}* orbitals perturbed by interactions with the substituents and into substituent \textgreek{s}* orbitals. N substituents give a substantial splitting and destabilization of the benzene LUMO (\textgreek{p}4,5*), while P and As substituents cause little splitting and a slight stabilization of this orbital. Virtual orbital eigenvalues from min.-basis-set SCF-MO calcns. on the monosubstituted benzenes show the same trends. Redn. in the p character of the substituent lone pair, redn. in the magnitude of interactions, and increased stabilization of the benzene LUMO's by mixing with the substituent \textgreek{s}* orbitals along the N $\rightarrow$ As series may all contribute to this trend. Similarly, O substituents give a substantial \textgreek{p}4*-\textgreek{p}5* splitting while S substituents give primarily an inductive stabilization of the \textgreek{p}4,5* orbitals. [on SciFinder(R)]Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzenehttps://puma.ub.uni-stuttgart.de/bibtex/2dd247d6e4f6157daed586230a3310cbf/b_schwederskib_schwederski2019-07-15T13:41:23+02:0015 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Judith C. Giordan" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/0"><span itemprop="name">J. Giordan</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="John H. Moore" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/1"><span itemprop="name">J. Moore</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="John A. Tossell" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/2"><span itemprop="name">J. Tossell</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang. Kaim" itemprop="url" href="/person/17ea5294591d4c545467db27eed86711c/author/3"><span itemprop="name">W. Kaim</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Journal of the American Chemical Society</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">107 </span></span>(<span itemprop="issueNumber">20</span>):
<span itemprop="pagination">5600--5604</span></em> </span>(<em><span>1985<meta content="1985" itemprop="datePublished"/></span></em>)</span>Mon Jul 15 13:41:23 CEST 2019Journal of the American Chemical Society205600--5604Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzene107198515 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission Electron-transmission spectroscopy was used to det. the energies of low-lying neg.-ion states of MenM (M = N, P, As, n = 3; M = O, S, n = 2) as well as p-(MenM)2C6H4 (M = N, As, n = 3; M = O, S, n = 2). Spectral peaks are obsd., corresponding to electron capture into benzene \textgreek{p}* orbitals perturbed by interactions with the substituents and into substituent \textgreek{s}* orbitals. N substituents give a substantial splitting and destabilization of the benzene LUMO (\textgreek{p}4,5*), while P and As substituents cause little splitting and a slight stabilization of this orbital. Virtual orbital eigenvalues from min.-basis-set SCF-MO calcns. on the monosubstituted benzenes show the same trends. Redn. in the p character of the substituent lone pair, redn. in the magnitude of interactions, and increased stabilization of the benzene LUMO's by mixing with the substituent \textgreek{s}* orbitals along the N $\rightarrow$ As series may all contribute to this trend. Similarly, O substituents give a substantial \textgreek{p}4*-\textgreek{p}5* splitting while S substituents give primarily an inductive stabilization of the \textgreek{p}4,5* orbitals. [on SciFinder(R)]