Reactivity of Indene, Fluorene, Azulene, and Acenaphthylene with a Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Dihydride
详细信息 查看全文
- 作者：Javier A. Cabeza ; Ignacio del Rí ; o ; José ; M. Ferná ; ndez-Colinas ; Pablo Garcí ; a-Á ; lvarez ; Daniel Miguel
- 刊名：Organometallics
- 出版年：2007
- 出版时间：March 12, 2007
- 年：2007
- 卷：26
- 期：6
- 页码：1414 - 1423
- 全文大小：318K
- 年卷期：v.26,no.6(March 12, 2007)
- ISSN：1520-6041
文摘
The basal-edge-bridged square-pyramidal hexanuclear cluster [Ru6(
3-H)2(5-
2-ampy)(-CO)2(CO)14](1; H2ampy = 2-amino-6-methylpyridine) reacts with indene in refluxing chlorobenzene to give [Ru7(3-H)(5-2-ampy)(-
9-C9H7)(-CO)3(CO)11] (2), [Ru6(3-H)(5-2-ampy)(5-C9H7)(3-CO)(-CO)2(CO)11] (3), and the known dimer [Ru2(5-C9H7)2(-CO)2(CO)2]. While the indenyl ligand of complex 2is 5:6 edge bridging, complex 3 has a terminal 5-indenyl ligand. The hexanuclear 6-fluorene derivative[Ru6(3-H)2(5-2-ampy)(6-C13H10)(-CO)2(CO)11] (4) has been isolated from a reaction of compound1 with fluorene in decane at reflux temperature. Under analogous conditions, azulene reacts with 1 togive [Ru6(5-2-ampy)(3-10-C10H8)(-CO)2(CO)10] (5) and [Ru4(3-10-C10H8)(CO)9] (6). In bothcomplexes, the azulene ligand is attached to three Ru atoms through its ten C atoms. Four complexeshave been isolated from reactions of acenaphthylene with complex 1 in refluxing decane: [Ru4(4-2-ampy)(-6-C12H8)(-4-C12H8)(-CO)2(CO)5] (7), [Ru6(4-2-ampy)(3-10-C12H8)(CO)12] (8), [Ru7(5-2-ampy)(4-12-C12H8)(-CO)(CO)12] (9), and [Ru6(4-1-ampy)(4-12-C12H8)(-CO)2(CO)9] (10). Thesecompounds do not maintain the metallic skeleton of the starting complex 1 and contain acenaphthyleneligands that display unprecedented coordination modes, such as 5:1 edge bridging (7), 2:2 edge bridging(7), 6:5:1 triangular face capping (8), and 5:3:2:2 quadruply bridging (9 and 10). The coordinationmode of the ampy ligand of compound 10, which has a 4-imido fragment and an uncoordinated pyridylgroup, is also unprecedented. The high temperatures required by all these reactions promote clusterdecarbonylation processes. This accounts for the observation that, with few exceptions (3, 4, 7), most ofthe reaction products contain the polycyclic hydrocarbon ligands attached to various metal atoms throughmany carbon atoms.
3-H)2(5-2-ampy)(-CO)2(CO)14](1; H2ampy = 2-amino-6-methylpyridine) reacts with indene in refluxing chlorobenzene to give [Ru7(3-H)(5-2-ampy)(-9-C9H7)(-CO)3(CO)11] (2), [Ru6(3-H)(5-2-ampy)(5-C9H7)(3-CO)(-CO)2(CO)11] (3), and the known dimer [Ru2(5-C9H7)2(-CO)2(CO)2]. While the indenyl ligand of complex 2is 5:6 edge bridging, complex 3 has a terminal 5-indenyl ligand. The hexanuclear 6-fluorene derivative[Ru6(3-H)2(5-2-ampy)(6-C13H10)(-CO)2(CO)11] (4) has been isolated from a reaction of compound1 with fluorene in decane at reflux temperature. Under analogous conditions, azulene reacts with 1 togive [Ru6(5-2-ampy)(3-10-C10H8)(-CO)2(CO)10] (5) and [Ru4(3-10-C10H8)(CO)9] (6). In bothcomplexes, the azulene ligand is attached to three Ru atoms through its ten C atoms. Four complexeshave been isolated from reactions of acenaphthylene with complex 1 in refluxing decane: [Ru4(4-2-ampy)(-6-C12H8)(-4-C12H8)(-CO)2(CO)5] (7), [Ru6(4-2-ampy)(3-10-C12H8)(CO)12] (8), [Ru7(5-2-ampy)(4-12-C12H8)(-CO)(CO)12] (9), and [Ru6(4-1-ampy)(4-12-C12H8)(-CO)2(CO)9] (10). Thesecompounds do not maintain the metallic skeleton of the starting complex 1 and contain acenaphthyleneligands that display unprecedented coordination modes, such as 5:1 edge bridging (7), 2:2 edge bridging(7), 6:5:1 triangular face capping (8), and 5:3:2:2 quadruply bridging (9 and 10). The coordinationmode of the ampy ligand of compound 10, which has a 4-imido fragment and an uncoordinated pyridylgroup, is also unprecedented. The high temperatures required by all these reactions promote clusterdecarbonylation processes. This accounts for the observation that, with few exceptions (3, 4, 7), most ofthe reaction products contain the polycyclic hydrocarbon ligands attached to various metal atoms throughmany carbon atoms.