E. I. Smyslova

Syntheses of organogold(1+) compounds by direct auration

Abstract Organogold(1+) compounds have been synthesized by direct auration of cyclopentadiene, cyanoacetic ester and malonitrile with (Ph 3 PAu) 3 O + BF 4 − . An X-ray structural study (λ Mo, 5062 reflections, R = 0.039) of bis(triphenylphosphinegold)malonitrile has been carried out (monoclinic, a = 12.055(6), b = 14.086(5), c = 20.466(12) A, β = 90.32(4)°, space group P 2 1 / c , Z = 4). The Auue5f8Au bond length is 2.912(1) A.

Cyanomethyl derivatives of gold

Conclusions1.Triphenylphosphine complexes of cyanomethylgold and dichlorocyanomethylgold have been synthesized.2.The chemical properties of aurated acetonitrile were typical for σ organogold compounds but aurated dichloroacetonitrile recalled the chemical behavior of complex gold halides3.The gold atom in the molecule of dichlorocyanomethyl (triphenylphosphine) gold has linear coordination, the bond lengths and angles were typical for organic complexes of univalent gold.

Reaction of gold compounds and diazomethane

1. n nWe discovered the reaction of inserting the methylene group at the gold-chlorine bond to give chloromethyl (triphenylphosphine) gold. n n n n n2. n nThe triphenylphosphine complexes of acetylacetonate-ferrocenyl-, and acetonylgold react with diazomethane to give vinyl(triphenylphosphine) gold. n n n n n3. n nThe reaction of chloromethyl(triphenylphosphine)gold with KI and NaCN gave, respectively, triphenylphosphinegold iodide and methyltriphenylphosphonium dicyanoaurate.

Reactions of vinyl(triphenylphosphine)gold

1. n nThe gold-carbon bond is cleaved when vinyl(triphenylphosphine)gold is treated with electrophilic reagents (acids, halides, mercury salts). n n n n n2. n nFluoboric acid converts vinyl(triphenylphosphine)gold to the fluoborate of the organogold complex cation, which contains two gold atoms. n n n n n3. n nThe treatment of vinyl(triphenylphosphine)gold with potassium permanganate in acetone gave the first member of theα-aurated ketones, namely triphenylphosphinegoldacetone.

Reactions of tris(triphenylphosphinegold)oxonium tetrafluoroboride with organolithium and organomagnesium compounds

ConclusionsTris(triphenylphosphinegold)oxonium tetrafluoroboride reacts with organolithium and organomagnesium compounds to give high yields of σ-organogold derivatives.