Experimental analysis demonstrates preferential binding and fluxional π-face exchange in a gold(I) π-allene complex, highlighting dynamic organometallic intermediate behavior.
The cationic gold π-allene complex {[P( t -Bu) 2 o -biphenyl]Au[η 2 -H 2 C═C═C(CH 3 ) 2 ]} + SbF 6 − was isolated in 98% yield from reaction of 3-methyl-1,2-butadiene with a mixture of [P( t -Bu) 2 o -biphenyl]AuCl and AgSbF 6 and was characterized by X-ray crystallography and variable-temperature NMR spectroscopy. These studies revealed preferential binding of gold to the less substituted C═C bond of the allene in both the solid state and solution and also revealed fluxional behavior consistent with π-face exchange of the allene ligand via an η 1 -C2 allene intermediate or transition state.
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Brown et al. (2010) studied this question.
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