Heterometallic TiIV–RuII and TiIV–ReIsulfato complexes containing the Kläui tripodal ligand [(η5-C5H5)Co{P(O)(OEt)2}3]−

Abstract

Treatment of [(L_OEt)₂Ti₂(μ-O)₂(μ-SO₄)] (L_OEt⁻ = [(η⁵-C₅H₅)Co{P(O)(OEt)₂}₃]⁻) with [Ru(H)(Cl)(CO)(PPh₃)₃] and Ag(OTf) (OTf⁻ = triflate) in the presence of Na₂CO₃ gave the Ti^IV–Ru^II complex [(L_OEt)₂Ti₂(μ-O)₃(μ₃-SO₄)Ru(CO)(PPh₃)₂] (2) whereas that with [Re(CO)₅(OTf)] afforded the Ti^IV–Re^I complex [H(L_OEt)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)]₃ have been determined. Complex 2 consists of an adamantane-like Ti₂RuSO₆ core, in which the {Ru^II(PPh₃)₂(CO)} moiety is facially coordinated to a tridentate-O,O′,O′′(sulfate) [(L_OEt)₂Ti₂(μ-O)₃(μ₃-SO₄)]²⁻ metalloligand. The anion [(L_OEt)₂Ti₂(μ-O)₃(μ-SO₄)Re(CO)₃(H₂O)]⁻ 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)₂Ti₂(μ-O)₃(μ-SO₄)]²⁻ metalloligand.