Three-coordinate monoanions of rhodium(1–) and iridium(1–): Isolable examples of coordinatively-unsaturated metalate anions
Three-coordinate monoanions of rhodium(1–) and iridium(1–): Isolable examples of coordinatively-unsaturated metalate anions
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铑(1-) 和铱(1-) 的三配位单阴离子：配位不饱和金属阴离子的可分离实例
DOI：
10.1016/j.poly.2023.116565
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发表时间：
2023
期刊：
影响因子：
2.6
通讯作者：
Figueroa, Joshua S.
中科院分区：
文献类型：
--
作者：
Neville, Michael L.;Chan, Chinglin;Barnett, Brandon R.;Hernandez, Ritchie E.;Moore, Curtis E.;Figueroa, Joshua S.
金属络合物-具有形式上负氧化态的金属中心的那些-通常是配位和电子饱和的有机金属物质。这些络合物中金属中心的还原性质被充分理解为是它们作为金属基亲核试剂的高反应性的原因。虽然这种配合物的化学性质是广泛的，但很少有配位或电子不饱和度伴随着高度约化的d轨道流形作为增加反应性的手段的例子。本文报道的是16 e-，d10铑和铱的金属阴离子，[M（CNArDipp 2）3]-，其中配位不饱和是通过使用双三联苯异腈配体实现的分离。与亲电试剂的反应性研究表明，在这些金属化物的Rh和Ir中心保留显着的亲核特性，这使得不寻常的金属/主族元素物种的形成，由于低配位数。
Metalate complexes – those that possess metal centers in formally negative oxidation states – are typically coordinatively and electronically saturated organometallic species. The reduced nature of the metal centers within these complexes is well understood to be responsible for their high reactivity as metal-based nucleophiles. While the chemistry of such complexes is extensive, there are very few examples where coordinative or electronic unsaturation accompanies highly-reduced d-orbital manifolds as a means to augment reactivity. Reported here is the isolation of the 16e–, d10rhodium and iridium metalate anions, [M(CNArDipp2)3]–, where coordinative unsaturation is achieved through the use of encumberingm-terphenyl isocyanide ligands. Reactivity studies with electrophiles demonstrate that the Rh and Ir centers in these metalates retain significant nucleophilic character, which enables the formation of unusual metal/main-group-element species on account of low coordination numbers.