Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph₃PAu⁺

Abstract

Deprotonated Fischer-type aminocarbene complexes, (CO)5M=C(NR2)CH3 (M = Cr or W; R = Me or propyl), react with Ph3PAu+ by metal group substitution - (CO)5M for Ph3PAu+--and attachment of the extricated M(CO)5 to the deprotonated methyl group. (The products may also be seen as aminovinylgold compounds coordinated to M(CO)5 moieties.) DFT calculations at the B3LYP level of theory using model compounds indicate a clear preference of the gold unit for central C to terminal coordination in the ligand [NMe2CCH2]-, whereas the Cr(CO)5 has a 7 kcal mol(-1) preference for C(vinyl) coordination compared to N-coordination. In related thiocarbenes, the sulfur donor atom should be the preferred point of attachment for the metal carbonyl unit. The latter prediction is borne out in practice, and in the three products isolated, including Ph3PAu{C(=CH2)SPh}Cr(CO)5 in a mixed crystal with [Ph3PAuSPh]Cr(CO)5, precisely this coordination mode is present. The latter component of the mixed crystal has also been prepared independently of the vinyl one.

Palladium‐Catalyzed Cross‐Coupling Reactions of Organogold(I) Reagents with Organic Electrophiles

“…Phenyl [18] Following the general procedure, a solution of phenylethynyllithium was prepared from phenylacetylene (20 mL, 0.182 mmol) and nBuLi (80 mL, 2.3 m in hexanes, 0.182 mmol) using a literature procedure. Butyl(triphenylphosphine)gold (1 c): [19] Following the general procedure, 1 c was isolated as a colorless oil (64.7 mg, 0.125 mmol, 83 %). 1 (E)-1-Hepten-1-yl(triphenylphosphine)gold (1 d): Following the general procedure, a solution of (E)-1-heptenyllithium, prepared from (E)-1iodo-1-heptene (40.8 mg, 0.182 mmol, E/Z 82:18) and tBuLi (0.215 mL, 1.7 m in pentane, 0.364 mmol), was added to a solution of [Ph 3 PAuCl] (90 mg, 0.182 mmol) in THF (3 mL) and the resulting organogold phosphane 1 d was used directly in the palladium-catalyzed cross-coupling re-action.…”

Pentacarbonyl[methyl(n-propylsulfanyl)carbene]chromium(0)

“…In our ongoing study of the chemistry of Fischer-type carbene complexes, we have focused on the utilization of simple derivatives as organometallic synthons (Raubenheimer et al, 2002(Raubenheimer et al, , 2005. In a recent report (Raubenheimer et al, 2006), we discussed the reaction of deprotonated thiocarbene complexes with the electrophile Ph 3 PAu + to afford mercaptovinyl complexes of Au that are S-coordinated to the M(CO) 5 (M = Cr, W) unit of the original Fischer carbene complex. Since structural information on the starting thiocarbene complexes is limited, the structure of the title compound, (I), is reported here.…”

First π-linker featuring mercapto and isocyano anchoring groups within the same molecule: synthesis, heterobimetallic complexation and self-assembly on Au(111)

“…Compound 5 reacted with Cr(CO) 5 (THF) via its 2-NC end to form orange Cr 0 adduct 6 . No product featuring the thioether S → Cr(CO) 5 interaction 35 was documented in this reaction. The [(–NC)Cr(CO) 5 ] moiety of 6 tolerated the basic environment and subsequent acidification of the reaction mixture used to convert 6 into auburn organometallic thiol 7 , which constitutes 3a with its 2-NC terminus anchored to the 16-e – [Cr(CO) 5 ] fragment.…”