Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et4N][Tp*W(μ3-S)3(CuBr)3] and Various Nitrogen Donor Ligands

详细信息    查看全文

• 作者：Zhen-Hong Wei^&#8224 ; ; Hong-Xi Li^&#8224 ; ; Mei-Ling Cheng^&#8224 ; ; Xiao-Yan Tang^&#8224 ; ; Yang Chen^&#8224 ; ; Yong Zhang^&#8224 ; ; Jian-Ping La
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：April 6, 2009
• 年：2009
• 卷：48
• 期：7
• 页码：2808-2817
• 全文大小：540K
• 年卷期：v.48,no.7(April 6, 2009)
• ISSN：1520-510X

文摘

Assembly of a family of monomeric, dimeric, and polymeric W/Cu/S clusters from a precursor cluster [Et₄N][Tp*W(μ₃-S)₃(CuBr)₃] (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) (1) and various N-donor ligands was reported. The treatment of 1 with pyridine (py) or aniline (ani) in the presence of NH₄PF₆ afforded a cationic cluster [Tp*W(μ₃-S)₃Cu₃(py)₃(μ₃-Br)](PF₆) (2) and a neutral cluster [{Tp*W(μ₃-S)₃(CuBr)₃}(μ₆-Br){Tp*W(μ₃-S)₃Cu₃(ani)₃}]·4ani·0.5Et₂O (3·4ani·0.5Et₂O). On the other hand, the treatment of 1 with excess 4,4′-bipyridine (4,4′-bipy) or 1,2-bis(4-pyridyl)ethylene (bpee) followed by the addition of NH₄PF₆ led to the formation of a polymeric cluster {[Tp*W(μ₃-S)₃Cu₃(4,4′-bipy)₃(μ₃-Br)](PF₆)·H₂O}_n (4) and a neutral cluster [{Tp*W(μ₃-S)₃Cu₃Br₂}₂(bpee)]·0.5CH₂Cl₂ (5·0.5CH₂Cl₂). Meanwhile, analogous reactions of 1 with excess 1,2-bis(4-pyridyl)ethane (bpe) or 1,3-bis(4-pyridyl)propane (bpp) in DMF under the presence of NH₄PF₆ resulted in the formation of two polymeric clusters {[{Tp*W(μ₃-S)₃Cu₃(μ₃-Br)}₂(bpe)₃](PF₆)₂·MeCN}_n (6) and {[Tp*W(μ₃-S)₃Cu₃Br(μ₃-Br)(bpp)]·DMF}_n (7). Compounds 1−7 were characterized by elemental analysis, IR spectra, UV−vis spectra, ¹H NMR, electrospray ionization mass spectra, and X-ray crystallography. The anion of 1 has an incomplete cubanelike [Tp*W(μ₃-S)₃(CuBr)₃] structure, while the cation of 2 has a cubanelike [Tp*W(μ₃-S)₃Cu₃(μ₃-Br)] structure. Compound 3 may be viewed as having a corner-shared double cubanelike structure that consists of one [Tp*W(μ₃-S)₃Cu₃(ani)₃]²⁺ dication and one [Tp*W(μ₃-S)₃(CuBr)₃]⁻ anion linked by a μ₆-Br bridge. For 4, each [Tp*W(μ₃-S)₃Cu₃(μ₃-Br)] unit works as a pyramidal three-connecting node to connect its equivalent ones via three 4,4′-bipy bridges to yield a 2D (6,3) cationic network. Compound 5 has a dimeric structure in which two incomplete cubanelike [Tp*W(μ₃-S)₃Cu₃Br₂] cores are bridged with one bpee ligand. For 6, each dimeric [{Tp*W(μ₃-S)₃Cu₃(μ₃-Br)}₂(bpe)₂] unit is interconnected via a pair of bpe bridges to form a 1D zigzag cationic chain. Compound 7 has a 1D spiral chain in which each [Tp*W(μ₃-S)₃Cu₃Br(μ₃-Br)] core is interlinked by a couple of bpp bridges. The formation of 2−7 from the precursor cluster 1 through various N-donor ligands offers a new way to the design and assembly of the W/Cu/S clusters with interesting molecular and supramolecular arrays.