Crystal Structure and Ligand Mobility in Solution of cis-Dimethyl-bis(trimethylphosphine)gold(III) Complexes

Abstract

Complexes [Me 2 Au(PMe 3 ) 2 ] + X − with X = I and ClO 4 have been prepared by several conventional routes in good yields. The products are thermally stable and decompose above 130 • C with reductive elimination of ethane. The two salts crystallize as isomorphous orthorhombic dichloromethane solvates. The cations have the cis-configuration based on a crystallographically imposed C 2v symmetry. Owing to the trans influence of the tertiary phosphine ligands the Au-C bonds are significantly shorter than in standard reference cases. The cations are stacked in pairs of columns running parallel to the c axis of the unit cell with the Me 2 Au units oriented in opposite directions and slightly interlocked. The anions are inserted into the pockets formed by the four Me 3 P groups of each pair of neighbouring cations in the same column. The large channels between the double columns are filled by the solvent molecules, which could be localized for the perchlorate salt, but were disordered and deficient in the iodide case.

Role of ionic liquids in the efficient transfer of lithium by Cyanex 923 in solvent extraction system

“…From ESI‐MS analysis, no formation of the Cyanex 923 tetramer or polymer complex with Li was detected. A search of the Cambridge Structural Database showed that lithium is generally four‐coordinated with triphenylphosphine oxide in Tetrahedron (T d ) geometry, for example, tetrakis(Triphenylphosphine oxide)‐lithium bis(iodo)‐gold (CCDC 606391), tetrakis(Triphenylphosphine oxide)‐lithium bromide(CCDC 112351) . The three‐coordinated Li complex with Cyanex 923 may result from steric effect due to the long alkyl chain of Cyanex 923.…”

Scope and Mechanism of Cooperativity at the Intersection of Organometallic and Supramolecular Catalysis

“…The guest complex formed in the reaction of 3-I was consistent with bis­(trimethylphosphine) gold cation 9 ⊂ 1 , which was verified by encapsulation of independently synthesized 9 (eq ). …”