Formation of Heterobimetallic Complexes by Addition of d(10)-Metal Ions to [(Me(3)P)(x)M(2-C(6)F(4)PPh(2))(2)] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions

[Image: see text] Treatment of the bis(chelate) complexes trans-[M(κ(2)-2-C(6)F(4)PPh(2))(2)] (trans-1M; M = Ni, Pt) and cis-[Pt(κ(2)-2-C(6)F(4)PPh(2))(2)] (cis-1Pt) with equimolar amounts or excess of PMe(3) solution gave complexes of the type [(Me(3)P)(x)M(2-C(6)F(4)PPh(2))(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(PMe(3))]. Four different complex types [(Me(3)P)(2)M(μ-2-C(6)F(4)PPh(2))(2)M′Cl] (5MM′; M = Ni, Pt; M′ = Cu, Ag, Au), [(Me(3)P)M(κ(2)-2-C(6)F(4)PPh(2))(μ-2-C(6)F(4)PPh(2))M′Cl](x) (x = 1: 6MM′; M = Pt; M′ = Cu, Au; x = 2: 6PtAg), head-to-tail-[(Me(3)P)ClM(μ-2-C(6)F(4)PPh(2))(2)M′] (7MM′; M = Ni, Pt; M′ = Au), and head-to-head-[(Me(3)P)ClM(μ-2-C(6)F(4)PPh(2))(2)M′] (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.