Abstract
The title compound, [IrZnI2(C10H15)(C3H9P)2]·0.5C6H6 or [Cp*(PMe3)2Ir]-[ZnI2] (Cp* = cyclo-C5Me5) was obtained and characterized as its benzene solvate [Cp*(PMe3)2Ir]-[ZnI2]·0.5C6H6. The bimetallic complex in this structure contains the Lewis-acidic fragment ZnI2 bonded to the Lewis-basic fragment Cp*(PMe3)2Ir, with an Ir-Zn bond distance of 2.452 (1) Å. The compound was obtained by reacting [Cp*(PMe3)IrI2] with 2-Ad2Zn (2-Ad = 2-adamant-yl), resulting in the reduction of the IrIII complex and formation of the IrI-ZnII adduct. The crystal studied was a twin by non-merohedry with a refined BASF parameter of 0.223 (1).
Highlights
An intuitive way to create metal–metal bonds is by linking a Lewis-basic metal center to a Lewis-acidic metal center
Regarding the Lewis-basic fragment, it has been noted that electron-rich half-sandwich complexes can be considered ‘metal bases par excellence’ (Werner, 1983), and zinc dihalides are among the most well-known Lewis acids
While complexes are known where a zinc dihalide acts as a bridge between metals or where aggregation occurs to form multi-zinc clusters, a search of the Cambridge Crystallographic Database (Groom et al, 2016) revealed no example of a structurally characterized complex [CpR(L)(L0)M]-[ZnX2] (M = either Co, Rh, or Ir) with a terminal zinc dihalide
Summary
An intuitive way to create metal–metal bonds is by linking a Lewis-basic metal center to a Lewis-acidic metal center. While complexes are known where a zinc dihalide acts as a bridge between metals (iridium: Kimura et al, 2012) or where aggregation occurs to form multi-zinc clusters (rhodium and zinc: Molon et al, 2010), a search of the Cambridge Crystallographic Database (Groom et al, 2016) revealed no example of a structurally characterized complex [CpR(L)(L0)M]-[ZnX2] (M = either Co, Rh, or Ir) with a terminal (non-bridging) zinc dihalide It appears, that regardless of the ligand coordination sphere there is no single example of an unsupported iridum–zinc bond. The bimetallic complex in this structure is the formal adduct of the Lewis base Cp*(PMe3)2IrI and the Lewis acid ZnIII2, providing the first structural characterization within the large class of metal– metal-bonded compounds [CpR(L)(L0)M]-[ZnX2] (M = Co, Rh, or Ir, X = halide, L, L0 = neutral ligand). In [Cp*(PMe3)2Ir]-[ZnI2], there is a relatively short intramolecular C—HÁ Á ÁI interaction between H14B (on the C14 methyl group) and I1, with an HÁ Á ÁI contact distance of 3.06 A (this reported distance is based on the calculated position of H14B, which is placed at 0.98 Afrom C14 and at an angle C14—H14BÁ Á ÁI1 of 157); the C14Á Á ÁI1 distance is 3.977 (12) A
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