Akademik Veri Yönetim Sistemi
JOURNAL OF ORGANOMETALLIC CHEMISTRY, cilt.997, 2023 (SCI-Expanded)
Herein, [Ru(NHC)(p-cymene)Cl-2] (3) and [MCl(NHC)(cod)] (M=Rh (4) or Ir (5)) (cod=1,5-cyclooctadiene) complexes of a silyl-substituted N-heterocyclic carbene ligand (NHC) have been prepared by the transmetalation reaction between Ag-NHC (2) and corresponding starting metal compound. The characterization of the complexes has been completed by NMR spectroscopy and elemental analyses. Solid state structures of Ag- (2) and Rh-NHC (4) have also been determined by single crystal X-ray analysis. [RhCl(NHC)(CO)(2)] type bis-carbonyl complex (6) has also been prepared and CO stretching frequencies pointed the strong s-donor ability of the silyl-substituted NHC. The catalytic activity of all complexes have been examined in hydrosilylation of terminal alkynes. Among the complexes, Ir-NHC has been found out as active catalyst with around 90% conversion and beta-(Z) selectivity at room temperature. Further studies revealed that this complex is able to maintain its stability in catalytic reaction conditions, chemoselective to alkynes in the presence of alkenes, and operable in scale-up reactions. In contrast, bis-carbonyl Rh-NHC performed 82% beta-(Z) selectivity with full conversion of alkyne in first 4 h of reaction, but when reaction time was extended to 24 h, almost all beta-(Z) vinylsilane isomerised to thermodynamically more stable beta-(E). (c) 2023 Elsevier B.V. All rights reserved.