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The reaction of the base-stabilizedsilyliumylidene triflate [LSi(DMAP)]OTf(1·OTf; L = PhC(NtBu)2, DMAP = 4-dimethylaminopyridine) with [Rh(cod)Cl]2and W(CO)5THF afforded [{L(DMAP)Si}2{μ-Rh(μ-Cl)2Rh(cod)}](OTf)2(2) and [L(DMAP)Si→W(CO)5]OTf (3), respectively. Their crystal structures determined by X-ray crystallography showthat the silyliumylidene cation acts as a two-electron donor coordinatingto the rhodium and tungsten atoms. [ABSTRACT FROM AUTHOR]

2-Phosphaphenol (L) forms unusualcomplexes with copper and gold halides. With CuCl, a dimeric [L2CuCl]2complex is observed with L acting both asη1-P terminal and μ2-P bridgingligand and a copper–copper short contact of 2.549 Å. Withcopper bromide, a distorted infinite chain [L2CuBr]nis formed, whereas with copper iodide, thezigzag chain [L2CuI]nis observed.The phosphaphenol acts as a terminal ligand coating the CuX molecularwires. With gold chloride, a dimeric [LAuCl]2complex isformed, which is held by an aurophilic interaction at 3.132 Å. [ABSTRACT FROM AUTHOR]

Thereaction of a terminal alkyne (RCCH) and 2-aminopyridine (R′C5NH3NH2) with the dinuclear species [Cp*IrCl2]2afforded the cationic aminocarbene derivativesCp*Ir(Cl)[ C(CH2R)NHC5NH3R′] via a hydroamination and a ligand substitution. The reactionpathway has been examined through computational studies. [ABSTRACT FROM AUTHOR]