Synthesis and Characterisation of Sigma- and Pi-Bonded Metallaphosphacarboranes
Synthesis and Characterisation of Sigma- and Pi-Bonded Metallaphosphacarboranes
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Sigma-和 Pi-键合金属磷碳硼烷的合成和表征
DOI：
10.1002/zaac.201300157
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
McLellan R
中科院分区：
文献类型：
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作者：
McLellan R
以[7,8 - nido - CPB9H11] -为原料，脱质子后用金属碎片处理，合成了两种新的金属磷酸碳硼烷。从[HNMe3][7,8‐nido‐CPB9H11]脱质子开始，与{(indeyl)Co}2+源反应得到η‐键合的钴磷硼烷3‐（η‐C9H7）‐3,1,2‐closo‐CoCPB9H10(1)第一个“半夹心”3,1,2‐金属磷硼烷。indenyl配体构象in1 (cisoidbetween indenyl桥头堡碳原子和笼杂原子,笼子里的碳原子躺下面indenyl碳碳键)显示,phosphacarborane配体的结构反式作用最弱的碳,因此不同的顺序B > P > c从[HNC5H11] [7 8 nido应承担CPB9H11应承担]去质子化反应和半相当于Cl2[俄文(P公/甲基异丙基苯)]2提供了地理σ保税ruthenaphosphacarborane 8量{俄文(P量甲基异丙基苯)Cl (C5H11N)}高78 - nido - CPB9H11(2)是第一个用磷碳硼烷σ -键与金属结合的分子。
Two new metallaphosphacarboranes have been synthesised from [7, 8‐nido‐CPB9H11]–by deprotonation followed by treatment with a metal fragment. Starting with [HNMe3][7, 8‐nido‐CPB9H11] deprotonation and reaction with a source of {(indenyl)Co}2+affords the η‐bonded cobaltaphosphacarborane 3‐(η‐C9H7)‐3,1,2‐closo‐CoCPB9H10(1) the first “half‐sandwich“ 3,1,2‐metallaphosphacarborane. The indenyl ligand conformation in1(cisoidbetween the indenyl bridgehead carbon atoms and cage heteroatoms, with the cage carbon atom lying below the indenyl C–C bond) reveals that the structural trans effect in a phosphacarborane ligand is weakest for carbon and therefore varies in the order B > P > C. Starting with [HNC5H11][7, 8‐nido‐CPB9H11] deprotonation and reaction with half an equivalent of [Ru(p‐cymene)Cl2]2affords the σ‐bonded ruthenaphosphacarborane 8‐{Ru(p‐cymene)Cl(C5H11N)}‐7, 8‐nido‐CPB9H11(2), the first example of a molecule with a phosphacarborane σ‐bonded to a metal to be crystallographically characterised.