Tetrazolyl and tetrazolylidene complexes of gold: a synthetic and structural study

Lithiation of 1-benzyl-1H-tetrazole followed by transmetallation with [AuCl(PPh3)], [Au(C6F5)(tht)] or [AuCl(tht)] (tht = tetrahydrothiophene) and subsequent alkylation afforded cationic 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene(triphenylphosphine) gold(I), 1, neutral 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene(pentafluorophenyl) gold(I), 2, and a cationic biscarbene complex, bis(1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene) gold(I), 3. The first complex underwent a homoleptic rearrangement in solution to form 3. Reaction of [Au(N-3)PPh3] with the three isocyanides (CH3)(2)C6H3NC, (BuNC)-Bu-t and CyNC, respectively, yielded the corresponding neutral tetrazolyl(phosphine) complexes of gold, [1-(2,6-dimethylphenyl)-1H-tetrazol-5-yl](triphenylphosphine) gold(I), 4, [1-(tert-butyl)-1H-tetrazol-5-yl](triphenylphosphine) gold(I), 6, and [1-(cyclohexyl)-1H-tetrazol-5-yl]-(triphenylphosphine) gold(I), 7. Alkylation of 4 with methyl triflate on N-4 allowed isolation of the crystalline carbene complex 1-(2,6-dimethylphenyl)-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5ylidene) (triphenylphosphine) gold(I), 5. Complex 7 was not isolable in pure form but converts by isocyanide substitution of triphenylphosphine into [1-cyclohexylisocyanide][1-(cyclohexyl)-1H-tetrazol-5-yl] gold(I), 8. From a product mixture of 7 and 8 the transformed molecules [(cyclohexylamino)(ethoxy) carbene](1-cyclohexyl-1H-tetrazol-5-yl) gold(I), 9, and [bis(cyclohexylamino) carbene](1-cyclohexyltetrazol-5-yl) gold(I), 10, co-crystallised spontaneously after a long time at -20 degrees C.