Cyclopentadienyl yttrium complexes with the [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] metalloligand

Abstract

The reactivity of the yttrium trichloride complex [Cl3Y{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (2) with a variety of main-group metal cyclopentadienyl reagents [M(C5H3R1R2)] (M = Li, Na, K, Tl) or [Mg(C5H5)2] has been investigated. Treatment of 2 with one equivalent of [Na(C5H5)] or [K(C5H4SiMe3)] gives the monocyclopentadienyl derivatives [(η5-C5H4R)Cl2Y{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (R = H (3), SiMe3 (4)). Analogous reaction of 2 with lithium [Li(C5H3R1R2)] or thallium [Tl(C5H5)] reagents (1 or 2 equivalents) leads to complexes [(η5-C5H3R1R2)2Y(μ-Cl)2M{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (M = Li, R1 = R2 = H (5), R1 = H, R2 = SiMe3 (6), R1 = R2 = SiMe3 (7); M = Tl, R1 = R2 = H (8)). Complex 2 reacts with [Mg(C5H5)2] to yield the ionic compound [(μ-Cl)3Mg2{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}2][{Y(η5-C5H5)2Cl}2(μ-Cl)] (9). In contrast to the metathesis of chloride ligands, the reaction of 2 with the lithium indenyl derivative [Li(C9H7)] at room temperature produces C9H8 and the precipitation of [Li(μ-Cl)3Y{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (10). Crystallization of 10 in pyridine affords the lithium-free [Cl2(py)2Y{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (11) complex. The X-ray crystal structures of 6 and 11 have been determined.