A thorium metallacyclopentadiene complex: a combined experimental and computational study
A thorium metallacyclopentadiene complex: a combined experimental and computational study
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钍金属环戊二烯络合物：实验和计算相结合的研究
DOI：
10.1039/c5dt00838g
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Walter, Marc D.
中科院分区：
文献类型：
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作者：
Fang, Bo;Hou, Guohua;Walter, Marc D.
全面研究了钍金属环戊二烯的合成、结构和反应活性。在二苯乙炔 (PhC CPh) 存在下，用钾石墨 (KC8) 还原 (eta(5)-C5Me5)(2)ThCl2 (1)，生成第一个钍金属环戊二烯络合物 (eta(5)-C5Me5)(2)Th(eta(2)-C4Ph4) (2)。密度泛函理论 (DFT) 研究表明 5f 轨道参与金属环戊二烯 Th-(eta(2)-C=C-C=C) 部分的键合。与钍金属环丙烯相比，配合物 2 对重氮烷烃和有机叠氮化物（例如 Me3SiCHN2、9-重氮芴和对甲苯基 N(3)）表现出明显不同的反应性，导致形成六元肼基配合物 (eta(5)-C5Me5)(2)Th[N(N=CHSiMe3)(C4Ph4)] (3) 和分别为 (eta(5)-C5Me5)(2)Th[N(N=C(C12H8))(C4Ph4)] (4) 和七元双(三氮烯基)络合物 (eta(5)-C5Me5)(2)Th[N(N=N(对甲苯基))(C4Ph4) N(N=N(对甲苯基))] (5)。
The synthesis, structure, and reactivity of a thorium metallacyclopentadiene were comprehensively studied. The reduction of (eta(5)-C5Me5)(2)ThCl2 (1) with potassium graphite (KC8) in the presence of diphenylacetylene (PhC CPh) yields the first thorium metallacyclopentadiene complex (eta(5)-C5Me5)(2)Th(eta(2)-C4Ph4) (2). Density functional theory (DFT) studies suggest that the 5f orbitals are involved in the bonding of the metallacyclopentadiene Th-(eta(2)-C=C-C=C) moiety. Compared to the thorium metallacyclopropene, complex 2 shows a distinctively different reactivity towards diazoalkanes and organic azides such as Me3SiCHN2, 9-diazofluorene and p-tolylN(3), leading to the formation of the six-membered hydrazido complexes (eta(5)-C5Me5)(2)Th[N(N=CHSiMe3)(C4Ph4)] (3) and (eta(5)-C5Me5)(2)Th[N(N=C(C12H8))(C4Ph4)] (4) and the seven-membered bis(triazenido) complex (eta(5)-C5Me5)(2)Th[N(N=N(p-tolyl))(C4Ph4) N(N=N(p-tolyl))] (5), respectively.