Dinuclear Pd-II/Pt-II complexes [M-2(phosphine)(n)(thio-ligand)(3)]Cl incorporating N,S-bridged pyridine-2-thiolate and benzimidazoline-2-thiolate

作者：Lobana Tarlok S; Sandhu Amanpreet K; Mahajan Rakesh K; Hundal Geeta; Gupta Sushil K; Butcher Ray J; Castineiras Alfonso

来源：Polyhedron, 2017, 127: 25-35.

DOI：10.1016/j.poly.2017.01.042

• Pyridine-2-thione
• 1,3-Benzimidazoline-2-thione
• 1,3-Imidazoline-2-thione
• Palladium(II) chloride
• Platinum

Equimolar reaction of [PdCl2(dppm)] {dppm = bis(diphenylphosphino) methane) with pyridine-2-thione (pySH) in presence of NaOH base in aqueous ethanol formed dinuclear mixed-ligand complex, [Pd-2(II)(mu-kappa(2): N,S-pyS)(3)(mu-P,P-dppm)]Cl 1. Similarly, reaction of PdCl2(PPh3)(2) with benzimidazoline-2-thione (bzimSH) in 1:2 M ratio in the presence of Et3N base in acetonitrile has formed a dinuclear complex, [Pd-2(II)(mu-kappa(2):N,S-bzims)(2()kappa(1)-S-bzims)(PPh3)(3)]Cl center dot 2H(2)O 2. Surprisingly, analogous thio-ligand, 1,3-imidazoline-2-thione (imzSH), merely formed a simple square planar complex, [Pd(kappa(1)-S-imzSH)(4)]Cl-2.2H(2)O 3. The reaction of H2PtCl6 with pySH and dppm (1:1:1 M ratio) in the presence of Et3N base in toluene-ethanol (1:1:: v/v) mixture also formed a mixed-ligand dinuclear complex [Pt-2(II)(mu-kappa(2):N,S-pyS)(3)(mu-P,P-dppm)]Cl similar to 1. All these complexes have been characterized using analytical data, IR, NMR (H-1, P-31), UV-vis, fluorescence, ESI-mass and single crystal X-ray crystallographic techniques. The anionic thio-ligands are N,S-bridged in complexes 1 and 4, both N,S-bridged and kappa(1)-S bonded in 2 and as neutral k(1)-S bonded in 3. There are short M center dot center dot center dot M contacts in 1 and 4 (1: 2.7249(5) angstrom; 4: 2.7350(8) angstrom). Complexes 1, 3 and 4 showed intense fluorescence. ESI mass spectral studies of 1, 3 and 4 revealed the formation of molecular ions and other species.

• 出版日期2017-5-8