Monomeric, dimeric and polymeric W/Cu/S clusters based on [Et4N][Tp*W(mu3-S)3(CuBr)3] and various nitrogen donor ligands.

Assembly of a family of monomeric, dimeric, and polymeric W/Cu/S clusters from a precursor cluster [Et(4)N][TpW(mu(3)-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 NH(4)PF(6) afforded a cationic cluster Tp*W(mu(3)-S)(3)Cu(3)(py)(3)(mu(3)-Br) (2) and a neutral cluster [{TpW(mu(3)-S)(3)(CuBr)(3)}(mu(6)-Br){TpW(mu(3)-S)(3)Cu(3)(ani)(3)}] x 4 ani x 0.5 Et(2)O (3 x 4 ani x 0.5 Et(2)O). 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 NH(4)PF(6) led to the formation of a polymeric cluster {Tp*W(mu(3)-S)(3)Cu(3)(4,4'-bipy)(3)(mu(3)-Br) x H(2)O}(n) (4) and a neutral cluster [{TpW(mu(3)-S)(3)Cu(3)Br(2)}(2)(bpee)] x 0.5 CH(2)Cl(2) (5 x 0.5 CH(2)Cl(2)). 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 NH(4)PF(6) resulted in the formation of two polymeric clusters {[{TpW(mu(3)-S)(3)Cu(3)(mu(3)-Br)}(2)(bpe)(3)](PF(6))(2) x MeCN}(n) (6) and {[TpW(mu(3)-S)(3)Cu(3)Br(mu(3)-Br)(bpp)] x DMF}(n) (7). Compounds 1-7 were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, electrospray ionization mass spectra, and X-ray crystallography. The anion of 1 has an incomplete cubanelike [TpW(mu(3)-S)(3)(CuBr)(3)] structure, while the cation of 2 has a cubanelike [TpW(mu(3)-S)(3)Cu(3)(mu(3)-Br)] structure. Compound 3 may be viewed as having a corner-shared double cubanelike structure that consists of one Tp*W(mu(3)-S)(3)Cu(3)(ani)(3) dication and one Tp*W(mu(3)-S)(3)(CuBr)(3) anion linked by a mu(6)-Br bridge. For 4, each [TpW(mu(3)-S)(3)Cu(3)(mu(3)-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 [TpW(mu(3)-S)(3)Cu(3)Br(2)] cores are bridged with one bpee ligand. For 6, each dimeric [{TpW(mu(3)-S)(3)Cu(3)(mu(3)-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(mu(3)-S)(3)Cu(3)Br(mu(3)-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.