Synthesis and crystal structures of dimeric W(Mo)/Cu/S and polymeric W/Cu/S neutral clusters with flexible 1,4-bis(3,5-dimethylpyrazol-1-yl)butane as a linker ligand

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• 作者：Azizolla  ; Beheshti^a ;   ; ^{beheshti_a@hotmail.com} ; William  ; Clegg^b ;   ; ^{w.clegg@ncl.ac.uk} ;   ; ^{w.clegg@newcastle.ac.uk} ; Seyed A.  ; Mousavi Fard^a ; Ross W.  ; Harrington^b ; Valiollah  ; Nobakht^a ; Luca  ; Russo^b
• 关键词：Copper(I) complexes ; Flexible N-donor ligands ; Heterothiometallic clusters ; Polymeric compounds ; Crystal structure
• 刊名：Inorganica Chimica Acta
• 出版年：2011
• 出版时间：1 October 2011
• 年：2011
• 卷：376
• 期：1
• 页码：310-316
• 全文大小：448 K
• ISSN：S0020169311005330

文摘

Reactions of [MES₃]^{2?/sup> (M = W, Mo; E = S, O) with CuCl and bbd [1,4-bis(3,5-dimethylpyrazol-1-yl)butane] in DMF affords two new double nest-shape clusters, [WOS₃Cu₃Cl(μ-bbd)]₂ (1) and [MoOS₃Cu₃Cl(μ-bbd)]₂ (2) and a novel one-dimensional polymeric complex [WS₄Cu₂(μ-bbd)]_n (4). The complexes have been characterized by elemental analysis, IR and UV–Vis spectroscopy, and single-crystal X-ray diffraction. In the core structure of the isostructural dimeric [MOS₃Cu₃Cl(μ-bbd)]₂ clusters, the copper atoms have a distorted trigonal planar geometry, with CuS₂N and CuS₂Cl core environments. The [MOS₃Cu₃] fragments are interconnected by a pair of flexible μ-bbd ligands via their nitrogen donor atoms to form a centrosymmetric macrocyclic twin-nest-shaped cluster in which the two fragments are also linked by direct secondary Cu…Cl interactions. Complex 4 represents the first example of a polymeric heterothiometallic cluster, interconnected by bbd ligands, to be structurally characterized by X-ray crystallography. In the repeat unit of 4, the skeleton of the cluster core [CuS₂WS₂Cu] has an essentially linear Cu…W…Cu arrangement. The W atom retains the tetrahedral geometry of the parent [WS₄]2?/sup> anion. These cluster cores are linked by bbd bridges having alternately two different conformations to construct a zigzag structure. Complexes [MoS₄Cu₃Cl(bbd)_0.5]₂ (3) and [WS₄Cu₄(NCS)₂(bbd)₂]_n (5) have been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy, but we have been unable to grow suitable crystals of 3 and 5 for X-ray analysis.}