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

Treatment of the bis(chelate) complexes -[M(κ -2-C F PPh ) ] ( - ; M = Ni, Pt) and -[Pt(κ -2-C F PPh ) ] ( - ) with equimolar amounts or excess of PMe solution gave complexes of the type [(Me P) M(2-C F PPh ) ] ( = 2: , = 1: , ; M = Ni, Pt). The reactivity of complexes of the type and toward monovalent coinage metal ions (M' = Cu, Ag, Au) was investigated next to the reaction of toward [AuCl(PMe )]. Four different complex types [(Me P) M(μ-2-C F PPh ) M'Cl] ( ; M = Ni, Pt; M' = Cu, Ag, Au), [(Me P)M(κ -2-C F PPh )(μ-2-C F PPh )M'Cl] ( = 1: ; M = Pt; M' = Cu, Au; = 2: ), head-to-tail-[(Me P)ClM(μ-2-C F PPh ) M'] ( ; M = Ni, Pt; M' = Au), and head-to-head-[(Me P)ClM(μ-2-C F PPh ) M'] ( ; M = Ni, Pt; M' = Cu, Ag, Au) were observed. Single-crystal X-ray analyses of complexes - 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.