%0 Journal Article %1 Giordan.1985 %A Giordan, Judith C. %A Moore, John H. %A Tossell, John A. %A Kaim, Wolfgang. %D 1985 %J Journal of the American Chemical Society %K 15 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission %N 20 %P 5600--5604 %R 10.1021/ja00306a003 %T Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzene %V 107 %X 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 p* orbitals perturbed by interactions with the substituents and into substituent s* orbitals. N substituents give a substantial splitting and destabilization of the benzene LUMO (p4,5*), 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 s* orbitals along the N $\rightarrow$ As series may all contribute to this trend. Similarly, O substituents give a substantial p4*-p5* splitting while S substituents give primarily an inductive stabilization of the p4,5* orbitals. on SciFinder(R)

@article{Giordan.1985, abstract = {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)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Giordan, Judith C. and Moore, John H. and Tossell, John A. and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2dd247d6e4f6157daed586230a3310cbf/huebleriac}, doi = {10.1021/ja00306a003}, interhash = {7ea5294591d4c545467db27eed86711c}, intrahash = {dd247d6e4f6157daed586230a3310cbf}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {15 16 16;methide Group MO;MO VA VIA affinity electron methide methide;electron spectra transmission}, number = 20, pages = {5600--5604}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Interaction of frontier orbitals of Group 15 and Group 16 methides with the frontier orbitals of benzene}, volume = 107, year = 1985 }