Formation of Heterobimetallic Complexes by Addition of d10-Metal Ions to [(Me3P)xM(2-C6F4PPh2)2] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions

Robert Gericke; Martin A Bennett; Steven H Privér; Suresh K Bhargava

doi:10.1021/acs.inorgchem.3c00311

Formation of Heterobimetallic Complexes by Addition of d¹⁰-Metal Ions to [(Me₃P)_xM(2-C₆F₄PPh₂)₂] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions

Inorg Chem. 2023 Jun 12;62(23):8846-8862. doi: 10.1021/acs.inorgchem.3c00311. Epub 2023 May 31.

Authors

Robert Gericke^{1

2}, Martin A Bennett³, Steven H Privér¹, Suresh K Bhargava¹

Affiliations

¹ Centre for Advanced Materials and Industrial Chemistry, School of Applied Sciences (Applied Chemistry), RMIT University, GP.O. Box 2476, Melbourne, Victoria 3001, Australia.
² Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf e. V., Bautzner Landstraße 400, Dresden 01328, Germany.
³ Research School of Chemistry, Australian National University, Canberra ACT 2601, Australia.

Abstract

Treatment of the bis(chelate) complexes trans-[M(κ²-2-C₆F₄PPh₂)₂] (trans-1M; M = Ni, Pt) and cis-[Pt(κ²-2-C₆F₄PPh₂)₂] (cis-1Pt) with equimolar amounts or excess of PMe₃ solution gave complexes of the type [(Me₃P)_xM(2-C₆F₄PPh₂)₂] (x = 2: 2M^a, 2M^b x = 1: 3M^a, 3M^b; M = Ni, Pt). The reactivity of complexes of the type 2M and 3M toward monovalent coinage metal ions (M' = Cu, Ag, Au) was investigated next to the reaction of 1M toward [AuCl(PMe₃)]. Four different complex types [(Me₃P)₂M(μ-2-C₆F₄PPh₂)₂M'Cl] (5MM'; M = Ni, Pt; M' = Cu, Ag, Au), [(Me₃P)M(κ²-2-C₆F₄PPh₂)(μ-2-C₆F₄PPh₂)M'Cl]_x (x = 1: 6MM'; M = Pt; M' = Cu, Au; x = 2: 6PtAg), head-to-tail-[(Me₃P)ClM(μ-2-C₆F₄PPh₂)₂M'] (7MM'; M = Ni, Pt; M' = Au), and head-to-head-[(Me₃P)ClM(μ-2-C₆F₄PPh₂)₂M'] (8MM'; M = Ni, Pt; M' = Cu, Ag, Au) were observed. Single-crystal X-ray analyses of complexes 5-8 revealed short metal-metal separations (2.7124(3)-3.3287(7) Å), suggestive of attractive metal-metal interactions. Quantum chemical calculations (atoms in molecules (AIM), electron localization function (ELF), non-covalent interaction (NCI), and natural bond orbital (NBO)) gave theoretical support that the interaction characteristics reach from a pure attractive non-covalent to an electron-shared (covalent) character.