Direct Synthesis and Bonding Properties of the First μ²-η²,η²-Allyl-Bridged Diiridium Complex

Abstract

The direct synthesis of the first μ(2)-η(2),η(2)-allyl-bridged diiridium complex ([2](+)), bearing the uncommon counterion [IrCl2(COD)](-) ([3](-)), is described. Both bridging moieties in [2](+), namely, allyl and acetate, are introduced in a single reaction step from [{IrCl(COD)}2] (1) and allyl acetate. A combination of X-ray crystallography and density functional theory calculations reveals pronounced metal-allyl π-back-bonding.

Zwitterionic Rhodium and Iridium Complexes Based on a Carboxylate Bridge-Functionalized Bis-N-heterocyclic Carbene Ligand: Synthesis, Structure, Dynamic Behavior, and Reactivity

“…As observed in the solid-state structure of 14 , the square planar anion [IrCl 2 (cod)] − is similar to that already described for related compounds (see Supporting Information). − The iridium­(III) cation [IrCl­(cod)­{κ 3 C,C′,O-(MeIm) 2 COO}] + in 14 exhibits a distorted octahedral coordination polyhedron with a κ 3 C,C′,O coordination mode of the tridentate ligand. The coordination of the iridium center is completed by the bidentate cod ligand and one chlorido, trans to the oxygen atom [O(1)–Ir(1)–Cl(1) 168.15(13)°, Figure ].…”

“…In fact, reaction of [(MeIm) 2 is similar to that already described for related compounds (see Supporting Information). 53,54,55 The iridium(III) cation [IrCl(cod){κ 3 35 Notably as a consequence of the κ 3 C,C',O coordination of the bis-NHC ligand, the interplanar angles (Table 2) of the 6-member ring Ir-C(1)-N(5)-C(7)-N(9)-C(10) as well as the yaw angles { 9.8, C(1); 9.0, C(10)} of the imidazole-2-carbene moieties are bigger than those of the related rhodium(I) derivative 11 (vide supra) and of the previously reported 35 complex Ir(cod){κ 2 C,C'-(MeIm) 2 COO}. The mass spectrum and the spectroscopic data for 14 are in agreement with the structure found in the solid state.…”