Cyclopentadienyl and Alkynyl Copper(I) Derivatives with the [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] Metalloligand

Abstract

The treatment of [ClCu{(mu(3) NH)(3)Ti-3(eta(5) C5Me5)(3)(mu(3) N)}] (2) with lithium cyclopentadienide in toluene at room temperature affords [(C5H5)Cu{(mu(3) NH)(3)Ti-3(eta(5) C5Me5)(3)(mu(3) N)}] (4) where the cyclopentadienyl ligand is bound to copper(l) in an eta(2) fashion The analogous reaction of 2 with lithium acetylides [Li(C equivalent to CR)] gives complexes [(RC equivalent to C)Cu{(mu(3) NH)(3) (eta(5) C5Me5)(3)(mu(3) N)}] (R = SiMe3 (5) Ph (6)) with terminal alkynyl ligands bound to copper Compound 6 is prepared in higher yield by the treatment of [{Ti(eta(5) C5Me5)(mu NH)}(3)(mu(3) N)] (1) with [Cu(C equivalent to CPh)] in toluene at room temperature The cyclopentadienyl derivative 4 decomposes in solution to generate the edge linked double cube nitrido complex [{Cu(mu(4) N)(mu(3) NH)(2)Ti-3(eta(5) C5Me5)(3)(mu(3) N)}(2)] (3) via C5H6 elimination However solutions of the alkynyl derivatives 5 and 6 lead to copper(I) acetylide bridged double cube complexes [{Cu(mu 1 kappa C-1 2 kappa C-1 C equivalent to CR)Cu(mu(4) N)(mu(3) NH)(2)Ti-3(eta(5) C5Me5)(3)(mu(3) N)}(2)] (R = SiMe3 (7) Ph (8)) along with 1 and RC equivalent to CH The X ray crystal structures of 4 5 7 and 8 have been determined