Han Jaehong, Coucouvanis Dimitri
The Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055, USA.
Inorg Chem. 2002 May 20;41(10):2738-46. doi: 10.1021/ic010913+.
The reactions of the (Et(4)N)(2)[(Cl(4)-cat)(MeCN)MoFe(3)S(4)Cl(3)] (I) cluster with Fe(pp)(2)Cl(2) (pp = depe (bis(1,2-diethylphosphino)ethane) or dmpe (bis(1,2-dimethylphosphino)ethane)) produced the (Cl(4)-cat)MoFe(3)S(4)(pp)(2)Cl(mu-pp) (pp = depe (III) or dmpe (V)) singly bridged double cubanes. The reactions of I with the same bidentate phosphine ligands in the presence of NaBPh(4) also produced III and the (Cl(4)-cat)MoFe(3)S(4)(dmpe)(2)(mu-S)(mu-dmpe) (VI) doubly bridged double cubane, respectively. The byproduct (BPh(4))[Fe(dmpe)(2)(MeCN)Cl] (VII) has been isolated from the reaction mixture and crystallographically characterized. The depe analogue of VI, (Cl(4)-cat)MoFe(3)S(4)(depe)(2)(mu-S)(mu-depe) (IV), has been successfully prepared from III in the presence of excess Li(2)S. Similar reactions with (Et(4)N)(2)[Fe(4)S(4)(SPh)(4)] (VIII) have resulted in the formation of the neutral Fe(4)S(4)(depe)(2)(SPh)(2) (IX) cluster. The chloride analogue of IX, Fe(4)S(4)(depe)(2)Cl(2) (XI), has been obtained by a reaction of IX with benzoyl chloride. The crystal and molecular structures of III, VI, VII, and XI have been determined by single-crystal X-ray crystallography. The electrochemical and spectroscopic properties, including the Mossbauer spectra of the new clusters, have been determined and analyzed.
(Et(4)N)(2)[(Cl(4)-cat)(MeCN)MoFe(3)S(4)Cl(3)]（I）簇合物与Fe(pp)(2)Cl(2)（pp = depe（双（1,2 - 二乙基膦基）乙烷）或dmpe（双（1,2 - 二甲基膦基）乙烷））反应生成了(Cl(4)-cat)MoFe(3)S(4)(pp)(2)Cl(μ - pp)（pp = depe（III）或dmpe（V））单桥连双立方烷。I在NaBPh(4)存在下与相同的双齿膦配体反应，分别生成了III和(Cl(4)-cat)MoFe(3)S(4)(dmpe)(2)(μ - S)(μ - dmpe)（VI）双桥连双立方烷。副产物（BPh(4))[Fe(dmpe)(2)(MeCN)Cl]（VII）已从反应混合物中分离出来并通过晶体学表征。在过量Li(2)S存在下，由III成功制备了VI的depe类似物(Cl(4)-cat)MoFe(3)S(4)(depe)(2)(μ - S)(μ - depe)（IV）。与(Et(4)N)(2)[Fe(4)S(4)(SPh)(4)]（VIII）的类似反应导致形成了中性的Fe(4)S(4)(depe)(2)(SPh)(2)（IX）簇合物。通过IX与苯甲酰氯反应得到了IX的氯化物类似物Fe(4)S(4)(depe)(2)Cl(2)（XI）。通过单晶X射线晶体学确定了III、VI、VII和XI的晶体和分子结构。已确定并分析了新簇合物的电化学和光谱性质，包括穆斯堡尔谱。
