Reactivity of Arenes, Cycloheptatriene, and Dicyclopentadiene with a Basal Edge-Bridged Square Pyramidal Hexaruthenium Dihydride
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- 作者：Javier A. Cabeza ; Ignacio del Rí ; o ; Pablo Garcí ; a-Á ; lvarez ; and Daniel Miguel
- 刊名：Organometallics
- 出版年：2006
- 出版时间：May 8, 2006
- 年：2006
- 卷：25
- 期：10
- 页码：2683 - 2692
- 全文大小：364K
- 年卷期：v.25,no.10(May 8, 2006)
- ISSN：1520-6041
文摘
The reactions of 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) with arenes at high temperature (>110 
C)give [Ru6(3-H)2(5-2-ampy)(
6-arene)(-CO)2(CO)11] (arene = C6H6 2a, C6H5Me 2b, 1,4-C6H4Me2 2c).These complexes result from the substitution of the arene for the three CO ligands of the apical Ru atomof 1. Cycloheptatriene reacts with complex 1 in chlorobenzene at reflux temperature to give a mixtureof products from which the hexanuclear cluster complexes [Ru6(3-H)(5-2-ampy)(5-C7H9)(3-CO)(-CO)2(CO)11] (3), [Ru6(3-H)(5-2-ampy)(3-7-C7H7)(-CO)2(CO)11] (4), [Ru6(5-2-ampy)(2-7-C7H7)2(-CO)(CO)9] (5), and [Ru6(6-C)(3-7-C7H7)2(-CO)2(CO)8] (6) have been isolated and characterized.While compound 3 has a terminal 5-cycloheptadienyl ligand, 4 contains a face-capping 5:2-cycloheptatrienyl ligand, and 5 has two edge-bridging 4:3-cycloheptatrienyl ligands. Compound 6, aminor product of this reaction, contains an octahedral metallic skeleton with a 6-carbide and two face-capping 3:2:2-cycloheptatrienyl ligands. It has been established that the thermolysis of complex 3gives 4 and that complex 5 arises from the reaction of 4 with cycloheptatriene. Treatment ofdicyclopentadiene with complex 1 in chlorobenzene at reflux temperature has allowed the isolation of[Ru2(5-C5H5)2(-CO)2(CO)2] and three cluster derivatives, [Ru6(3-H)(5-2-ampy)(5-C5H5)(3-CO)(-CO)2(CO)11] (7), [Ru6(3-H)2(5-2-ampy)(5-C5H5)2(3-CO)(-CO)(CO)9] (8), and [Ru5(5-2-ampy)(4-4-C10H10)(-CO)2(CO)10] (9). Compounds 7 and 8 are hexanuclear and contain one and two terminalcyclopentadienyl ligands, respectively. The pentanuclear derivative 9 features an unprecedented 2:2-enyne ligand that derives from the activation of two adjacent H-C(sp2) bonds of dicyclopentadiene.With the exception of compounds 6 and 9, the remaining clusters have the same Ru6(5-2-ampy)framework as compound 1 and have the apical Ru atom attached to hydrocarbon ligands.
3-H)2(5-2-ampy)(-CO)2(CO)14] (1; H2ampy = 2-amino-6-methylpyridine) with arenes at high temperature (>110 C)give [Ru6(3-H)2(5-2-ampy)(6-arene)(-CO)2(CO)11] (arene = C6H6 2a, C6H5Me 2b, 1,4-C6H4Me2 2c).These complexes result from the substitution of the arene for the three CO ligands of the apical Ru atomof 1. Cycloheptatriene reacts with complex 1 in chlorobenzene at reflux temperature to give a mixtureof products from which the hexanuclear cluster complexes [Ru6(3-H)(5-2-ampy)(5-C7H9)(3-CO)(-CO)2(CO)11] (3), [Ru6(3-H)(5-2-ampy)(3-7-C7H7)(-CO)2(CO)11] (4), [Ru6(5-2-ampy)(2-7-C7H7)2(-CO)(CO)9] (5), and [Ru6(6-C)(3-7-C7H7)2(-CO)2(CO)8] (6) have been isolated and characterized.While compound 3 has a terminal 5-cycloheptadienyl ligand, 4 contains a face-capping 5:2-cycloheptatrienyl ligand, and 5 has two edge-bridging 4:3-cycloheptatrienyl ligands. Compound 6, aminor product of this reaction, contains an octahedral metallic skeleton with a 6-carbide and two face-capping 3:2:2-cycloheptatrienyl ligands. It has been established that the thermolysis of complex 3gives 4 and that complex 5 arises from the reaction of 4 with cycloheptatriene. Treatment ofdicyclopentadiene with complex 1 in chlorobenzene at reflux temperature has allowed the isolation of[Ru2(5-C5H5)2(-CO)2(CO)2] and three cluster derivatives, [Ru6(3-H)(5-2-ampy)(5-C5H5)(3-CO)(-CO)2(CO)11] (7), [Ru6(3-H)2(5-2-ampy)(5-C5H5)2(3-CO)(-CO)(CO)9] (8), and [Ru5(5-2-ampy)(4-4-C10H10)(-CO)2(CO)10] (9). Compounds 7 and 8 are hexanuclear and contain one and two terminalcyclopentadienyl ligands, respectively. The pentanuclear derivative 9 features an unprecedented 2:2-enyne ligand that derives from the activation of two adjacent H-C(sp2) bonds of dicyclopentadiene.With the exception of compounds 6 and 9, the remaining clusters have the same Ru6(5-2-ampy)framework as compound 1 and have the apical Ru atom attached to hydrocarbon ligands.