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Updated: Feb 25, 2026
Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Systematic Study of N-Heterocyclic Carbene Coordinate Hydrosilylene Transition-Metal Complexes
Carsten Eisenhut1, Tibor Szilvási2, Gizem Dübek3
1Institut für Chemie, Technische Universität Berlin , Straße des 17 Juni 135, Sekr. C2, D-10623 Berlin, Germany.
Abstract:
An in-depth study of the synthesis and structures of N-heterocyclic carbene (NHC)-stabilized silylene transition-metal complexes is reported. An iron hydrosilylene complex, [tBu3Si(NHC)(H)Si:→Fe(CO)4] (2), was synthesized starting from the corresponding hydrosilylene [tBu3Si(NHC)(H)Si:] (1). Complex 2 was fully characterized, including X-ray diffraction analysis, which showed an unusual long Si-Fe bond length. A very long bond length was also observed in the novel hydrosilylene tungsten complex [tBu3Si(NHC)(H)Si:→W(CO)5] (3). A series of NHC-stabilized silylene iron complexes ([R2(NHC)Si:→Fe(CO)4], where R = Cl (4), H (5), and Me (6)) were synthesized and fully characterized to investigate the influence of different substituents. The dihydrosilylene iron complex [H2(NHC)Si:→Fe(CO)4] (5) represents a new example of a donor-acceptor-stabilized parent silylene (H2Si:). Density functional theory calculations were utilized to understand the influence of the electronic and steric effects of the silylene unit and its substituents on the Si-Fe bond in these iron complexes, in particular to rationalize the long Si-Fe bond in 2.
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