Heterometallic TiIV–RuIIand TiIV–ReIsulfato complexes containing the Kläui tripodal ligand [(η5-C5H5)Co{P(O)(OEt)2}3]−CCDC reference numbers 760949and 760950. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c001604g

Treatment of [(LOEt)2Ti2(μ-O)2(μ-SO4)] (LOEt−= [(η5-C5H5)Co{P(O)(OEt)2}3]−) with [Ru(H)(Cl)(CO)(PPh3)3] and Ag(OTf) (OTf−= triflate) in the presence of Na2CO3gave the TiIV–RuIIcomplex [(LOEt)2Ti2(μ-O)3(μ3-SO4)Ru(CO)(PPh3)2] (2) whereas that with [Re(CO)5(OTf)] afforded the TiIV–ReIcomplex [H(LOEt)2Ti2(μ-O)3(μ-SO4)Re(CO)3(H2O)] (3). The crystal structures of complexes 2·HOTf and [3·2/3(Et3NHOTf)·5/12(H2O)]3have been determined. Complex 2consists of an adamantane-like Ti2RuSO6core, in which the {RuII(PPh3)2(CO)} moiety is facially coordinated to a tridentate-O,O′,O′′(sulfate) [(LOEt)2Ti2(μ-O)3(μ3-SO4)]2−metalloligand. The anion [(LOEt)2Ti2(μ-O)3(μ-SO4)Re(CO)3(H2O)]−in 3can be viewed as consisting of a fac-{ReI(CO)3} fragment coordinated with one aqua ligand and a bidentate-O,O′-[(LOEt)2Ti2(μ-O)3(μ-SO4)]2−metalloligand. [ABSTRACT FROM AUTHOR]