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

The reactivity of the yttrium trichloride complex [Cl3Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-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 [(eta(5)-C5H4R)Cl2Y{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (R = H (3), SiMe3 (4)). Analogous reaction of 2 with lithium [Li((C5H3RR2)-R-1)] or thallium [Tl(C5H5)] reagents (1 or 2 equivalents) leads to complexes [(eta(5)-(C5H3RR2)-R-1)(2)Y(mu-Cl)(2)M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Li, R-1 = R-2 = H (5), R-1 = H, R-2 = SiMe3 (6), R-1 = R-2 = SiMe3 (7); M = Tl, R-1 = R-2 = H (8)). Complex 2 reacts with [Mg(C5H5)(2)] to yield the ionic compound [(mu-Cl)(3)Mg-2{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)][{Y(eta(5)-C5H5)(2)Cl}(2)(mu-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(mu-Cl)(3)Y{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (10). Crystallization of 10 in pyridine affords the lithium-free [Cl-2(py)(2)Y{(mu(3)-N)(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (11) complex. The X-ray crystal structures of 6 and 11 have been determined. (c) 2019 Elsevier B.V. All rights reserved.