Synthesis, Structure, and Reactivity of an NHC Silyl Gold(I) Complex

Abstract

The first example of a silyl gold(I) complex stabilized by an N-heterocyclic carbene (NHC) was synthesized and fully characterized, including crystallographically. The syn insertion of methyl propiolate into the Au−Si bond leading to a vinyl gold complex is reported. As substantiated by X-ray diffraction analysis, the reaction proceeds with opposite regioselectivity compared with that previously observed with phosphine silyl gold(I) complexes.

Transformation of Thiolatogold(I) to an Au Complex with an (Arylthio)silyl Ligand. Use of an (Aminosilyl)boronic Ester as a Silylene Precursor

“…The synthesis and properties of silylgold complexes have attracted attention . The reactions of organosilanes with Au­(I) complexes are expected to form the corresponding silylgold­(III) complexes, similar to the complexes of other d 10 metals, such as Pd(0) and Pt(0).…”

Syn-Insertion of Alkynes into Gold–Phosphito Bonds: Stereoselectivity and Reversible Protodeauration

“…Bourissou found that methyl propiolate regioselectively inserted into the gold–silicon bond of (Ph 3 P)­AuSiMe 2 Ph to generate a vinylgold species with a β-carboxylate fragment. , Subsequent work revealed that changing the supporting ligand to an N-heterocyclic carbene reversed the regioselectivity of the insertion reaction (Scheme ). Ananikov reported the acetic acid promoted insertion of methyl propiolate into the gold–phosphorus bond of gold thiolate compounds (Scheme ). …”

“…35,49 Subsequent work revealed that changing the supporting ligand to an N-heterocyclic carbene reversed the regioselectivity of the insertion reaction (Scheme 3). 60 Ananikov reported the acetic acid promoted insertion of methyl propiolate into the gold−phosphorus bond of gold thiolate compounds (Scheme 3). 61 To probe the reactivity of terminal alkynes toward the insertion reaction, a model gold phosphito compound (5) was treated with terminal alkynes.…”

Reactivity Studies of Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Phosphinidenide with AuCl

“…N-heterocyclic carbenes (NHCs) have been proven to be excellent ligands so far for the generation of two coordinate Au I complexes [1][2][3][4][5][6][7][8][9][10][11] consisting of mononuclear to polynuclear [2,4,7,9,10] metallic units with fascinating structural aspects, varied catalytic, [4] and photoluminescence (PL) properties. [7,10,11] The Au 11 -nanocluster reported by Narouz et al showed an improved electrochemical reduction of CO 2 to CO with coordination of an NHC ligand.…”