title: Reactivity Studies on a Binuclear Ruthenium(0) Complex Equipped with a Bridging κ(2)N,Ge-Amidinatogermylene Ligand.
abstract: The amidinatogermylene-bridged diruthenium(0) complex [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)7] (2; (i)Pr2bzam = N,N'-bis(iso-propyl)benzamidinate; HMDS = N(SiMe3)2) reacted at room temperature with (t)BuNC and PMe3 to give [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(L)(CO)6] (L = (t)BuNC, 3; PMe3, 4), which contain the new ligand in an axial position on the Ru atom that is not attached to the amidinato fragment. At 70 °C, 2 reacted with PPh3, PMe3, dppm, and dppe to give the equatorially substituted derivatives [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(L)(CO)6] (L = PPh3, 5; PMe3, 6) and [Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(μ-κ(2)P,P'-L2)(CO)5] (L2 = dppm, 7; dppe, 8). HSiEt3 and HSnPh3 were oxidatively added to complex 2 at 70 °C, leading to the coordinatively unsaturated products [Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)5] (ER3 = SiEt3, 9; SnPh3, 10), which easily reacted with (t)BuNC and CO to give the saturated derivatives [Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}((t)BuNC)(CO)5] (ER3 = SiEt3, 11; SnPh3, 12) and [Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)6] (ER3 = SiEt3, 13; SnPh3, 14), respectively. Compounds 9-14 have their ER3 group on the Ru atom that is not attached to the amidinato fragment. In contrast, the reaction of 2 with H2 at 70 °C led to the unsaturated tetranuclear complex [Ru4(μ-H)2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}2(CO)10] (15), which also reacted with (t)BuNC and CO to give the saturated derivatives [Ru4(μ-H)2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}2(L)2(CO)10] (L = (t)BuNC, 16; CO, 17). All tetraruthenium complexes contain an unbridged metal-metal connecting two germylene-bridged diruthenium units. Under CO atmosphere, complex 17 reverted to compound 2. All of the coordinatively unsaturated products (9, 10, and 15) have their unsaturation(s) located on the Ru atom(s) that is(are) attached to the amidinato fragment(s). In the absence of added reagents, the thermolysis of 2 in refluxing toluene led to [Ru4{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}{μ3-κGe-Ge(HMDS)}(μ-κ(3)N,C,N'-(i)Pr2bzam)(μ-CO)(CO)8] (18), which contains two new ligands, a triply bridging germylidyne and a bridging benzamidinate, and that results from the condensation of two molecules of 2 and the activation of the Ge-N bond of the benzamidinatogermylene ligand of 2.
authors.affiliation: †Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
authors.forename: Javier A
authors.initials: JA
authors.lastname: Cabeza
authors.affiliation: †Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
authors.forename: José M
authors.initials: JM
authors.lastname: Fernández-Colinas
authors.affiliation: †Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
authors.forename: Pablo
authors.initials: P
authors.lastname: García-Álvarez
authors.affiliation: †Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Pérez-Carreño
authors.affiliation: †Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
authors.forename: Diego
authors.initials: D
authors.lastname: Polo