%0 Journal Article %1 Roy.2015 %A Roy, Sudipta %A Dittrich, Birger %A Mondal, Totan %A Koley, Debasis %A Stueckl, A. Claudia %A Schwederski, Brigitte %A Kaim, Wolfgang %A John, Michael %A Vasa, Suresh Kumar %A Linser, Rasmus %A Roesky, Herbert W. %D 2015 %J Journal of the American Chemical Society %K DFT HOMO LUMO M06 carbene dimer ketenimine prepn structure %N 19 %P 6180--6183 %R 10.1021/jacs.5b03407 %T Carbene Supported Dimer of Heavier Ketenimine Analogue with P and Si Atoms %V 137 %X A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C=C=N-R) analog. The dark-red rod-shaped crystals of 2 were synthesized by redn. of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2$\rightarrow$P-Tip with sodium naphthalenide. The crystals of 2 are storable at room temp. for several months and stable up to 215 °C under an inert atm. X-ray single-crystal diffraction revealed that 2 contains a cyclic nonplanar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron redn. indicating the formation of the corresponding radical anion 2.bul.-, which was further characterized by EPR measurements in soln. The electronic structure and bonding of 2 and 2.bul.- were studied by theor. calcns. The exptl. obtained data are in good agreement with the calcd. values. [on SciFinder(R)]

@article{Roy.2015, abstract = {A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C=C=N-R) analog. The dark-red rod-shaped crystals of 2 were synthesized by redn. of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2$\rightarrow$P-Tip with sodium naphthalenide. The crystals of 2 are storable at room temp. for several months and stable up to 215 °C under an inert atm. X-ray single-crystal diffraction revealed that 2 contains a cyclic nonplanar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron redn. indicating the formation of the corresponding radical anion 2.bul.-, which was further characterized by EPR measurements in soln. The electronic structure and bonding of 2 and 2.bul.- were studied by theor. calcns. The exptl. obtained data are in good agreement with the calcd. values. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Roy, Sudipta and Dittrich, Birger and Mondal, Totan and Koley, Debasis and Stueckl, A. Claudia and Schwederski, Brigitte and Kaim, Wolfgang and John, Michael and Vasa, Suresh Kumar and Linser, Rasmus and Roesky, Herbert W.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/200a0e727c4b7946e5e1e15e899e3e0d7/huebleriac}, doi = {10.1021/jacs.5b03407}, interhash = {b52c57212a6160157e0a14a36a8a558e}, intrahash = {00a0e727c4b7946e5e1e15e899e3e0d7}, issn = {0002-7863}, journal = {Journal of the American Chemical Society}, keywords = {DFT HOMO LUMO M06 carbene dimer ketenimine prepn structure}, number = 19, pages = {6180--6183}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Carbene Supported Dimer of Heavier Ketenimine Analogue with P and Si Atoms}, volume = 137, year = 2015 }