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The isotypic crystal structures of two titanocene complexes containing an E Me 3 unit ( E = Al, Ga; Me = meth-yl) with two μ  2 -coordinating methyl groups, namely [μ-1(η 5 )-(adamantan-1-yl-2κ C  1 )cycylo-penta-dien-yl]di-μ 2 -methyl-methyl-2κ C -[1(η 5 )-penta-methyl-cyclo-penta-dien-yl]aluminiumtitanium(III), [AlTi(CH 3 ) 3 (C 10 H 15 )(C 15 H 18 )], and [μ-1(η 5 )-(adamantan-1-yl-2κ C  1 )cycylo-penta-dien-yl]di-μ 2 -methyl-methyl-2κ C -[1(η 5 )-penta-methyl-cyclo-penta-dien-yl]galliumtitanium(III), [GaTi(CH 3 ) 3 (C 10 H 15 )(C 15 H 18 )], are reported. Reacting a dinuclear nitro-gen-bridged low-valent titanium(III) complex with the Lewis acids AlMe 3 or GaMe 3 results in the loss of mol-ecular di-nitro-gen and the formation of two monomeric titanocene(III) fragments bearing two μ  2 -bridging methyl groups. Single crystal X-ray diffraction reveals the formation of a new E -C bond involving the penta-fulvene ligand while the bridging and terminal methyl groups remain intact.

Crystal structures of titanium–aluminium and –gallium complexes bearing two μ2 -CH3 units

Crystal structures of titanium–aluminium and –gallium complexes bearing two μ₂ -CH₃ units