| Sumario: | The reactivity of cis-bis(alkynyl)bis((diphenylphosphino)alkyne)platinum(II) complexes cis-[Pt(C≡CR)2L2] (R = Ph, But; L = PPh2C≡CPh (L1), PPh2C≡CBut (L2); 1-4), formed by displacement of the COD ligand from [Pt(C≡CR)2(COD)], toward cis-[M(C6F5)2(thf)2] (M = Pt, Pd, thf = tetrahydrofuran; in both a 1:1 and 1:2 molar ratio) has been investigated. Treatment of 1-4 with 1 equiv of cis-[M(C6F5)2(thf)2] affords dinuclear derivatives [{L2Pt-(μ-η1:η2-C≡CR) 2}M(C6F5)2] (5-12) with exclusive formation of doubly alkynyl-bridged systems. The molecular structure of [{(ButC≡CPh2P)2Pt(μ-η 1:η2-C≡CPh)2}Pd(C6F 5)2], 10, is presented. In contrast, it was found that the course of the reactions with 2 equiv of cis-[M(C6F5)2(thf)2] strongly depend on the alkynyl substituents and metal centers. Thus, treatment of tert-butylalkynyl derivatives cis-[Pt(C≡CBut)2L2] (2, 4) with 2 equiv of cis-[M(C6F5)2(thf)2] (M = Pt, Pd) only gives the expected trinuclear complexes 15A and 18A, in the case of the reactions with cis-[Pt(C6F5)2(thf)2]. The molecular structure of the complex [{Pt(μ-κ(P):η2-PPh2C≡CPh) 2(μ-η1:η2-C≡CBu t)2}{Pt(C6F5)2} 2], 15A, reveals that both the complexed cis-Pt(C6F5)2 moieties are symmetrically linked to the precursor "cis-[Pt(C≡CBut)2-(PPh 2C≡CPh)2]", with the platinum atoms connected by two unusual mixed alkynyl/ phosphinoalkyne bridging systems. On the other hand, similar reactions of phenylethynyl derivatives (1, 3) with 2 equiv of cis-[Pd(C6F5)2(thf)2] and 3 (L = PPh2C≡CBut) with cis-[Pt-(C6F5)2(thf)2] lead, instead, to the unexpected trinuclear PtPd2 (14B, 17B) and Pt3 (16B) derivatives which display terminal phosphinoalkyne ligands and, hence, contain the alkynyl groups acting as μ3-η2 (σ-Pt edge Pd or Pt) bridging ligands. However, a mixture of both types of isomers 13A and 13B (50:32) is observed in the reaction system cis-[Pt(C≡CPh)2-(PPh2C≡CPh)2] (1)/cis-[Pt(C6F5)2(thf)2]. The following order of bonding capability is deduced from this study: alkynyl > P-bonded phosphinoalkyne and XC≡CPh fragments > XC≡CBut (X = Pt, P).
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