Abstract
It has been shown in preceding experimental work that cyclometalated 6-benzylpyridines with gold(III) centers in the metallacycle (1) adopt a boat conformation reminiscent of the structure of 9,10-dihydroanthracene. There is a conspicuously short Au center dot center dot center dot H-C contact with a pseudoaxial methyl group suggesting a significant interaction which may be the prototype for (AuH)-H-III center dot center dot center dot-C hydrogen bonding. Quantum chemical calculations on the B3LYP/def2-TZVP level have now shown that the ground state structures and conformations adopted by the homologues with two hydrogen atoms, two methyl groups, and a hydrogen atom and a methyl group at the carbon atom bridging the two (hetero)arene rings can be explained on the basis of simple conformation rules. There is no evidence that the (AuH)-H-III center dot center dot center dot-C contact leads to an attractive interaction. The results are discussed in the context of literature data for Pt(II) analogues. Examples for potential (AuH)-H-III center dot center dot center dot-X interactions presented in other references appear to be of a similar character.