Heterometallic Ti~(IV)-Ru~(II) and Ti~(IV)-Re ~I sulfato complexes containing the Kl?ui tripodal ligand [(η~5-C_5H_5)Co{P(O)(OEt)_2} _3]~-

摘要

Treatment of [(L_(OEt))_2Ti_2(μ-O) _2(μ-SO_4)] (L_(OEt)~- = [(η~5-C_5H_5)Co{P(O)(OEt)_2} _3]~-) with [Ru(H)(Cl)(CO)(PPh_3)_3] and Ag(OTf) (OTf- = triflate) in the presence of Na_2CO _3 gave the Ti~(IV)-Ru~(II) complex [(L _(OEt))_2Ti_2(μ-O)_3(μ_3- SO_4)Ru(CO)(PPh_3)_2] (2) whereas that with [Re(CO)_5(OTf)] afforded the Ti~(IV)-Re~I complex [H(L_(OEt))_2Ti_2(μ-O)_3(μ-SO _4)Re(CO)_3(H_2O)] (3). The crystal structures of complexes 2·HOTf and [3·2/3(Et_3NHOTf)·5/ 12(H_2O)]_3 have been determined. Complex 2 consists of an adamantane-like Ti_2RuSO_6 core, in which the {Ru ~(II)(PPh_3)_2(CO)} moiety is facially coordinated to a tridentate-O,O′,O′′(sulfate) [(L_(OEt)) _2Ti_2(μ-O)_3(μ_3-SO _4)]~(2-) metalloligand. The anion [(L_(OEt)) _2Ti_2(μ-O)_3(μ-SO_4)Re(CO) _3(H_2O)]- in 3 can be viewed as consisting of a fac-{Re_I(CO)_3} fragment coordinated with one aqua ligand and a bidentate-O,O′-[(L_(OEt))_2Ti_2(μ-O) 3(μ-SO4)]~(2-) metalloligand.