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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Construction of trinuclear iridium clusters through ancillary ortho-carborane-1,2-diselenolato ligands, with simultaneous iridium-induced B-H activation
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Construction of trinuclear iridium clusters through ancillary ortho-carborane-1,2-diselenolato ligands, with simultaneous iridium-induced B-H activation

机译:通过辅助邻位-甲碳环-1,2-二硒代萘配体构建三核铱簇,同时铱诱导B-H活化

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The reaction of the 16-electron "pseudo-aromatic" complex Cp*Ir[Se2C2( B10H10)] ( 1, Cp* = eta(5)-C5Me5) with [ Ir( cod)(mu-OC2H5)](2) leads to the trinuclear iridium complexes {( cod) Ir[ Se2C2( B10H8)( OC2H5)]}Ir{[Se2C2( B10H10)] IrCp*} (2), {(cod) Ir[Se2C2( B10H8)( OC2H5)]} Ir{[ Se2C2( B10H9)] IrCp*} ( 3), {Cp* Ir[ Se2C2( B10H9)]}{IrSe2[ C-2( B10H9)( OC2H5)]}{[ Se2C2( B10H10)] IrCp*} ( 4) and one mononuclear complex Cp* Ir[ Se2C2( B10H8)( OC2H5)(2)] ( 5). The reactivity of 2 was investigated and revealed that transformation from 2 to 3 occurred thermally in solution. The transoid complex 2 ( with the carborane diselenolato units in trans position) can be converted in nearly 90% yield to the cisoid complex 3. In complexes 2, 3, two diselenolato carborane ligands bridge the Ir-3 core, which consists of Ir-Ir metal bonds. Compared with transoid 2, the cisoid 3 contains two iridium-boron bonds. Complex 4 consists of three different coordination environment carborane ligands ( Ir-B-cluster: {Cp*Ir[Se2C2( B10H9)]}, O-B-cluster: {[Se2C2( B10H9)]( OC2H5)}, and intact carborane: {Cp* Ir[ Se2C2 ( B10H10)]}) without the presence of a metal-metal bond. Analogous reaction of 1 with [ Ir( cod)( mu-OCH3)](2) results in formation of the trinuclear complex {Cp*Ir[ Se2C2( B10H9)]}{IrSe2[ C-2( B10H9)( OCH3)]}{[ Se2C2( B10H10)] IrCp*} ( 6) and mononuclear complex Cp* Ir[ Se2C2( B10H8)( OCH3)(2)] ( 7). The structures of 2, 3, 4, 5, 6 and 7 have been determined by crystallographic studies.
机译:16电子“伪芳族”络合物Cp * Ir [Se2C2(B10H10)](1,Cp * = eta(5)-C5Me5)与[Ir(cod)(mu-OC2H5)](2)的反应导致三核铱络合物{(cod)Ir [Se2C2(B10H8)(OC2H5)]} Ir {[Se2C2(B10H10)] IrCp *}(2),{(cod)Ir [Se2C2(B10H8)(OC2H5)] } Ir {[Se2C2(B10H9)] IrCp *}(3),{Cp * Ir [Se2C2(B10H9)]} {IrSe2 [C-2(B10H9)(OC2H5)]} {[Se2C2(B10H9)] IrCp * }(4)和一种单核络合物Cp * Ir [Se2C2(B10H8)(OC2H5)(2)](5)。研究了2的反应性,发现在溶液中从2到3发生了热转化。可以将反式类固醇2(具有碳硼烷二硒代壬酸酯单元处于反式位置)以接近90%的产率转化为类固醇复合物3。在配合物2、3中,两个二硒代乙炔碳硼烷配体桥接Ir-3核,该核由Ir- Ir金属键。与Transoid 2相比,cisoid 3包含两个铱-硼键。配合物4由三种不同的配位环境碳硼烷配体(Ir-B簇:{Cp * Ir [Se2C2(B10H9)]},OB簇:{[Se2C2(B10H9)](OC2H5)}和完整的硼烷:{ Cp * Ir [Se2C2(B10H10)]}),而没有金属-金属键的存在。 1与[Ir(cod)(mu-OCH3)](2)的类似反应导致形成三核配合物{Cp * Ir [Se2C2(B10H9)]} {IrSe2 [C-2(B10H9)(OCH3)] } {[Se2C2(B10H10)] IrCp *}(6)和单核络合物Cp * Ir [Se2C2(B10H8)(OCH3)(2)](7)。 2、3、4、5、6和7的结构已通过晶体学研究确定。

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