Cabeza Javier A, Fernández-Colinas José M, García-Álvarez Pablo, Pérez-Carreño Enrique, Polo Diego
†Departamento de Química Orgánica e Inorgánica-IUQOEM, and ‡Departamento de Química Física y Analítica, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
Inorg Chem. 2015 May 18;54(10):4850-61. doi: 10.1021/acs.inorgchem.5b00412. Epub 2015 May 6.
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.
脒基亚锗烯桥连的二钌(0)配合物[Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)7] (2; (i)Pr2bzam = N,N'-双(异丙基)苯脒; HMDS = N(SiMe3)2)在室温下与(t)BuNC和PMe3反应，生成[Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(L)(CO)6] (L = (t)BuNC, 3; PMe3, 4)，其中新配体处于Ru原子上未连接苯脒片段的轴向位置。在70 °C下，2与PPh3、PMe3、dppm和dppe反应，生成赤道取代衍生物[Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(L)(CO)6] (L = PPh3, 5; PMe3, 6)和[Ru2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(μ-κ(2)P,P'-L2)(CO)5] (L2 = dppm, 7; dppe, 8)。HSiEt3和HSnPh3在70 °C下氧化加成到配合物2上，生成配位不饱和产物[Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)5] (ER3 = SiEt3, 9; SnPh3, 10)，它们很容易与(t)BuNC和CO反应，分别生成饱和衍生物[Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}((t)BuNC)(CO)5] (ER3 = SiEt3, 11; SnPh3, 12)和[Ru2(ER3)(μ-H){μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}(CO)6] (ER3 = SiEt3, 13; SnPh3, 14)。化合物9 - 14的ER3基团位于Ru原子上未连接苯脒片段的位置。相比之下，2在70 °C下与H2反应生成不饱和四核配合物[Ru4(μ-H)2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}2(CO)10] (15)，它也与(t)BuNC和CO反应生成饱和衍生物[Ru4(μ-H)2{μ-κ(2)Ge,N-Ge((i)Pr2bzam)(HMDS)}2(L)2(CO)10] (L = (t)BuNC, 16; CO, 17)。所有四钌配合物都含有一个未桥连的金属 - 金属键，连接两个亚锗烯桥连的二钌单元。在CO气氛下，配合物17可逆转变为化合物2。所有配位不饱和产物(9、10和15)的不饱和位点都位于连接苯脒片段的Ru原子上。在没有添加试剂的情况下，2在回流甲苯中热解生成[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)，它包含两个新配体，一个三桥连的亚锗炔和一个桥连苯脒，由两个2分子缩合以及2的苯脒基亚锗烯配体的Ge - N键活化产生。
