Inorganic Chemistry, Vol.49, No.18, 8401-8410, 2010
Incorporation of Boron, Aluminum, and Gallium Derivatives into [{Ti(eta(5)-C5Me5)(mu-O)}(3)(mu(3)-CR)] (R = H, Me)
The synthesis and characterization of a family of alkyl and halide adducts of group 13 elements (B, Al, Ga), containing the mu(3)-alkylidyne oxo derivative ligands [{Ti(eta(5)-C5Me5)(mu-O)}(3)(mu(3)-CR)] [R = H (1), Me (2)], are presented. The compounds are synthesized by Lewis acid base reactions involving equimolecular amounts of 1 or 2 and alkyl [AIR'(3)] (R' = Me, Et, Ph) or halide derivatives [MX3] (M = B, X = Br; M = Al, X = Cl, Br, I; M = Ga, X = Cl, Br). The novel species [{E3M}(mu(3)-O)(mu-O)(2){Ti(eta(5)-C5Me5)}(3)(mu(3)-CR)] (3-8 and 11-21; R = H, Me; M = B, Al, Ga; E = alkyl, halide) exhibit coordination of 1 or 2 through one of the three oxygen atoms of the Ti3O3 ring to the metal center. In the case of the reaction of 2 with 2 equiv of [AlMe3], the complex [{MeAl}(mu(3)-O)(3){Ti(eta(5)-C5Me5)}(3)(mu(3)-CCH2-)] (9) containing the naked carbanion mu(3)-CCH2- was isolated with methane elimination. On the other hand, the derivative [{Br3B}(mu(3)-O)(mu-O)(2){Ti(eta(5)-C5Me5)}(3)(mu(3)-CMe)] (11) undergoes cleavage of the trinuclear structure to give [TiBr(eta(5)-C5Me5)}(mu-O){Ti(eta(5)-C5Me5)}(MeCBO2){TiBr2(eta(5)-C5Me5) }] (22). The crystalline structures of some of these products are also included in this paper.