RT info:eu-repo/semantics/article T1 Heterometallic complexes with cube-type [MTi3N4] cores containing Group 10 metals in a variety of oxidation states A1 Martínez Espada, Noelia A1 Mena Montoro, Miguel A1 Pérez Redondo, Adrián A1 Varela Izquierdo, Víctor A1 Yélamos Sánchez, Carlos K1 Chlorine compounds K1 Iodine K1 Nickel K1 Platinum K1 Toluene K1 Química K1 Chemistry AB Treatment of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] (1) with one equivalent of [Ni(cod)2] (cod = 1,5-cyclooctadiene) in toluene at 60-80°C and subsequent addition of diphenylacetylene, trans-stilbene or triphenylphosphane afforded the nickel(0) complexes [LNi{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (L = PhCCPh (2), PhCHCHPh (3), PPh3 (4)). The nickel(ii) complex [I2Ni{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-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{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (6). Compound 6 reacted immediately with chloroform-d1 to give the palladium dichloride derivative [Cl2Pd{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-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{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (8). Complex 6 reacted with two equivalents of dimethylacetylenedicarboxylate (dmad) to give the metallacyclopentadiene palladium(ii) complex [{(MeOOC)4C4}Pd{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-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{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (10). Compound 10 reacted with excess iodine to afford the platinum(iv) ionic derivative [I3Pt{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]2(I3)(I5) (11) via an intermediate platinum(ii) complex [I2Pt{(μ3-NH)2Ti3(η5-C5Me5)3(μ-NH)(μ3-N)}] (12). The X-ray crystal structures of 5, 8, 9 and 11 have been determined. SN 1477-9226 YR 2015 FD 2015-06-07 LK http://hdl.handle.net/10017/38235 UL http://hdl.handle.net/10017/38235 LA eng NO Ministerio de Ciencia e Innovación de España, Universidad de Alcalá, Ministerio de Educación y Ciencia de España DS MINDS@UW RD 28-mar-2024