Carbene supported dimer of heavier ketenimine analogue with p and si atoms.
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) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2→P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months and stable up to 215 °C under an inert atmosphere. 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 reduction indicating the formation of the corresponding radical anion 2(•-), which was further characterized by EPR measurements in solution. The electronic structure and bonding of 2 and 2(•-) were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values.
†Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 4, 37077 Göttingen, Germany.
Sudipta
S
Roy
∥Chemistry Department, University of Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
Birger
B
Dittrich
‡Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur 741246, India.
Totan
T
Mondal
‡Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur 741246, India.
Debasis
D
Koley
†Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 4, 37077 Göttingen, Germany.
A Claudia
AC
Stückl
§ Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Brigitte
B
Schwederski
§ Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
Wolfgang
W
Kaim
⊥Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstraße 2, 37077 Göttingen, Germany.
Michael
M
John
#Abtl. NMR-basierte Strukturbiologie, Max-Planck-Institut für Biophysikalische Chemie, Am Faßberg 11, 37077 Göttingen, Germany.
Suresh Kumar
SK
Vasa
#Abtl. NMR-basierte Strukturbiologie, Max-Planck-Institut für Biophysikalische Chemie, Am Faßberg 11, 37077 Göttingen, Germany.
Rasmus
R
Linser
†Institut für Anorganische Chemie, Georg-August-Universität, Tammannstraße 4, 37077 Göttingen, Germany.
Herbert W
HW
Roesky