Synthesis of heterometal cluster complexes by the reaction of cobaltadichalcogenolato complexes with groups 6 and 8 metal carbonyls.
Synthesis of heterometal cluster complexes by the reaction of cobaltadichalcogenolato complexes with groups 6 and 8 metal carbonyls.
复制标题
DOI：
10.1021/ic0513282
复制
发表时间：
2006-01
影响因子：
4.6
通讯作者：
Masaki Murata;S. Habe;S. Araki;K. Namiki;Teppei Yamada;Norikiyo Nakagawa;T. Nankawa;M. Nihei;J. Mizutani;M. Kurihara;H. Nishihara
中科院分区：
文献类型：
--
作者：
Masaki Murata;S. Habe;S. Araki;K. Namiki;Teppei Yamada;Norikiyo Nakagawa;T. Nankawa;M. Nihei;J. Mizutani;M. Kurihara;H. Nishihara
金属簇合物[{CPCO(S2C6H4)}2Mo(CO)2](Cp=ETA(5)-C5H5)(3)，[{CPCO(S2C6H4)}2W(CO)2](4)，[CPCO(S2C6H4)Fe(CO)3](5)，[CPCO(S2C6H4)Ru(CO)2(P(T)Bu3)](6)，[{CPCO(Se2C6H4)}2Mo(CO)2](7)，通过[CPCO(E2C6H4)](E=S，Se)与[M(CO)3(Py)3](M=Mo，W)、[Fe(CO)5]或[Ru(CO)3(P(T)Bu3)2]反应合成了[{CPCO(Se2C6H4)}(Se2C6H4)W(CO)2](8)，并对其晶体结构和物理性能进行了研究。在系列的三核6金属钴配合物中，3、4和7具有相似的结构，但W-Se配合物8从硫类似物4中消除了一个钴原子和一个环戊二烯基团，不满足18电子规则。核磁共振氢谱分析表明，COW双核配合物8是由结构类似于7的三核Co2W配合物生成的。三核簇合物3、4和7经历了准可逆的两步单电子还原反应，表明形成了混价配合物Co(III)M(0)Co(II)(M=Mo，W)。混合价态的热力学稳定性按4<；3<；7的顺序增加。在双核8金属钴配合物5和6中，CPCO(S_2C_6H_4)部分和金属羰基部分分别作为Lewis酸特征和碱特征，这取决于它们的光谱化学性质和氧化还原性质。配合物5经历了可逆的两步单电子还原，电子顺磁共振(EPR)研究表明，从Co(III)Fe(0)逐步还原为Co(III)Fe(-I)和Co(II)Fe(-I)。
Metalladichalcogenolate cluster complexes [{CpCo(S2C6H4)}2Mo(CO)2] (Cp = eta(5)-C5H5) (3), [{CpCo(S2C6H4)}2W(CO)2] (4), [CpCo(S2C6H4)Fe(CO)3] (5), [CpCo(S2C6H4)Ru(CO)2(P(t)Bu3)] (6), [{CpCo(Se2C6H4)}2Mo(CO)2] (7), and [{CpCo(Se2C6H4)}(Se2C6H4)W(CO)2] (8) were synthesized by the reaction of [CpCo(E2C6H4)] (E = S, Se) with [M(CO)3(py)3] (M = Mo, W), [Fe(CO)5], or [Ru(CO)3(P(t)Bu3)2], and their crystal structures and physical properties were investigated. In the series of trinuclear group 6 metal-Co complexes, 3, 4, and 7 have similar structures, but the W-Se complex, 8, eliminates one cobalt atom and one cyclopentadienyl group from the sulfur analogue, 4, and does not satisfy the 18-electron rule. 1H NMR observation suggested that the CoW dinuclear complex 8 was generated via a trinuclear Co2W complex, with a structure comparable to 7. The trinuclear cluster complexes, 3, 4, and 7, undergo quasi-reversible two-step one-electron reduction, indicating the formation of mixed-valence complexes Co(III)M(0)Co(II) (M = Mo, W). The thermodynamic stability of the mixed-valence state increases in the order 4 < 3 < 7. In the dinuclear group 8 metal-Co complexes, 5 and 6, the CpCo(S2C6H4) moiety and the metal carbonyl moiety act as a Lewis acid character and a base character, respectively, as determined by their spectrochemical and redox properties. Complex 5 undergoes reversible two-step one-electron reduction, and an electron paramagnetic resonance (EPR) study indicates the stepwise reduction process from Co(III)Fe(0) to form Co(III)Fe(-I) and Co(II)Fe(-I).