Treatment of the bis(chelate) complexestrans-[M(κ2-2-C6F4PPh2)2]
(trans-1M; M = Ni, Pt) andcis-[Pt(κ2-2-C6F4PPh2)2] (cis-1Pt) with equimolar
amounts or excess of PMe3solution gave complexes of the
type [(Me3P)xM(2-C6F4PPh2)2] (x=
2:2Ma,2Mbx= 1:3Ma,3Mb; M = Ni,
Pt). The reactivity of complexes of the type2Mand3Mtoward monovalent coinage metal ions (M′ = Cu, Ag,
Au) was investigated next to the reaction of1Mtoward
[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 complexes5–8revealed
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.