Copper(I) and silver(I) complexes supported by the tridentate [{Ti(η(5)-C5Me5)(μ-NH)}3(μ3-N)] metalloligand

Copper(I) and silver(I) ionic compounds [(L)M{(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}][O(3)SCF(3)] containing [MTi(3)N(4)] cube-type cations have been prepared by reaction of [(CF(3)SO(2)O)M{(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}] (M = Cu (2), Ag (3)) with a variety of donor molecules L. Treatment of complexes 2 and 3 with NH(3) in toluene at room temperature gives the ammonia adducts [(H(3)N)M{(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}][O(3)SCF(3)] (M = Cu (4), Ag (5)), whose X-ray crystal structures reveal two cube-type cations associated through hydrogen bonding interactions between the ammine ligands and one oxygen atom of each trifluoromethanesulfonate anion. Analogous treatment of 2 and 3 with 1 equiv of pyridine, 2,6-dimethylphenylisocyanide, tert-butylisocyanide, or triphenylphosphane gives the ionic compounds [(L)M{(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}][O(3)SCF(3)] (L = py, M = Cu (6), Ag (7); L = CNAr, M = Cu (8), Ag (9); L = CNtBu, M = Cu (10), Ag (11); L = PPh(3), M = Cu (12), Ag (13)). The reactions of 2 and 3 with methylenebis(diphenylphosphane) (dppm) in a 1:1 ratio lead to the single-cube complexes [(dppm)M{(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}][O(3)SCF(3)] (M = Cu (14), Ag (15)), whereas in a 2:1 ratio give the bisphosphane-bridged double-cube compounds [{M(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}(2)(μ-dppm)][O(3)SCF(3)](2) (M = Cu (16), Ag (17)). Similarly, treatment of 2 or 3 with a half equivalent of ethane-1,2-diylbis(diphenylphosphane) (dppe) affords double-cube derivatives [{M(μ(3)-NH)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-N)}(2)(μ-dppe)][O(3)SCF(3)](2) (M = Cu (18), Ag (19)). The X-ray crystal structures of 4, 5, 10, 14, 15, and 18 have been determined.