Heterometallic complexes with cube-type [MTi3N4] cores containing Group 10 metals in a variety of oxidation states

Treatment of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with one equivalent of [Ni(cod)(2)] (cod = 1,5-cyclooctadiene) in toluene at 60-80 degrees C and subsequent addition of diphenylacetylene, trans-stilbene or triphenylphosphane afforded the nickel(0) complexes [LNi{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (L = Ph CPh (2), PhCH=CHPh (3), PPh3 (4)). The nickel(II) complex [I2Ni{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (5) was prepared by analogous addition of iodine to the solution obtained from the heating of 1 and [Ni(cod)(2)]. Treatment of 1 with one equivalent of [Pd(dba)(2)] (dba = dibenzylideneacetone) in toluene at room temperature led to the palladium(0) complex [(dba)Pd{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (6). Compound 6 reacted immediately with chloroform-d(1) to give the palladium dichloride derivative [Cl2Pd{(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu-NH)-(mu(3)-N)}] (7), which was prepared by treatment of 1 with [PdCl2(cod)] at room temperature. Addition of iodine to a toluene solution of 6 afforded the analogous palladium(II) derivative [I2Pd{(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu-NH)(mu(3)-N)}] (8). Complex 6 reacted with two equivalents of dimethylacetylenedicarboxylate (dmad) to give the metallacyclopentadiene palladium(II) complex [{(MeOOC)(4)C-4}Pd{(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu-NH)(mu(3)-N)}] (9) via oxidative coupling. The treatment of 1 with [Pt(nbe)(3)] (nbe = norbornene) in toluene at room temperature gave the platinum(0) complex [(nbe)Pt{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (10). Compound 10 reacted with excess iodine to afford the platinum(IV) ionic derivative [I3Pt{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu-N)}](2)(I-3)(I-5) (11) via an intermediate platinum(II) complex [I2Pt{(mu(3)-NH)(2)Ti-3(eta(5)-C5Me5)(3)(mu-NH)(mu(3)-N)}] (12). The X-ray crystal structures of 5, 8, 9 and 11 have been determined.