Silylene complexes from a stable silylene and metal carbonyls: synthesis and structure of [Ni{(Bu^tN–CHCH–NBu^t)Si}₂(CO)₂], a donor-free bis-silylene complex

Synthesis of the Sterically Related Nickel Gallanediyl Complexes [Ni(CO)3(GaAr′)] (Ar′ = C6H3-2,6-(C6H3-2,6-iPr2)2) and [Ni(CO)3(GaL)] (L = HC[C(CH3)N(C6H3-2,6-iPr2)]2): Thermal Decomposition of [Ni(CO)3(GaAr′)] to give the Cluster [Ni4(CO)7(GaAr′)3]

“…Interestingly, the nonequivalence of the isopropyl groups in the solid state cannot be observed in solution. The 13 C NMR spectra in benzene-D 6 display one signal for carbonyl and also one signal for both isopropyl groups, indicating a high fluxionality in 4 on the NMR time scale, similar to that observed 2 and analogous Ni(CO) 2 (L) 2 complexes [42,43]. The IR showed two characteristic stretching signals at 2039 (A 1 ) and 1,967 cm -1 (B 1 ), confirming that GaL is a ligand with good r-donor and poor p-acceptor qualities.…”

“…Reactions of GaL with Ni(CO) 4 : Synthesis and Structure of Ni(CO) 3 (GaL) (3) and Ni(CO) 2 (GaL) 2 (4) Reaction of GaL with Ni(CO) 4 at room temperature in benzene or hexane led to an immediate evolution of CO and formation of the nickel complex Ni(CO) 3 Ni ( [42,43]. To unambiguously characterize this compound single crystals were grown for an X-ray diffraction analysis.…”

Silver‐Catalyzed Silylene Transfer

“…40,41 Exposure of unsaturated silylene 16 to Ni(CO) 4 resulted in the formation of the disilylene-substituted tetrahedral nickel complex 17 (Scheme 7.3). 42,43 Similarly, mixing Ph 3 PAuCl with decamethylsilicocene 18 produced the silylgold complex 19. 44 The 29 Si { 1 H} NMR spectrum of 19 (d 78 ppm) revealed its silylenoid character.…”

Steric effects on the dialkyl substituted X2C2Si silylenes: A theoretical study

“…Chemical species which involve divalent silicon atoms, silylenes, are key intermediates in numerous thermal and photochemical reactions of organosilicon compounds [4]. Besides, much interest has been focused on their bonding properties and reactivities such as addition to olefins [11,12], alkynes [13], isocyanides [14], and transition metal complexes [15] in connection with the reactivities of carbenes. The multiple-bond compounds including second period elements such as olefin, imine (Schiff base), ketone, acetylene, nitrile, etc.…”