链状三核钼(钨)硫原子簇化合物[M_3O_2S_8]^(2-)的合成、光谱和晶体结构

Synthesis, Spectrum and Crystal Structures of the Chain Unsymmetrical Molybdenum-Sulfur and Tungsten-Sulfur Clusters [M_3O_2S_8]^(2-)

本文以[NH_4]_2MO_nS_(4-n)(M=Mo、W,n=0-2)为原料,在酸性和中性条件下,合成出九个新的三核不对称钼硫和钨硫原子簇状化合物L_2[M_3O_2S_8][L=(n-Bu)_4N、Ph_4P、PyC_(16)H_(33)、(CH_3)_3NC_(16)H_(33)、Et_4N]。用元素分析、红外光谱、紫外光谱对簇合物进行了表征,并测定了其中 [(n-Bu)_4N]_2[Mo_3O_2S_8](1)和[(n-Bu)_4N]_2[W_3O_2S_8](5)两个簇合物的晶体结构,簇合物1和5均属单斜晶系,P2_1/c空间群,簇合物1的晶胞参数:a=15.910(2),b=15.411(1),c=20.407(5)A,β=103.40°(1),V=4867.5A^3,Z=4,最终偏离因子R=0.060。簇合物5的晶胞参数。a=15.896(4),b=15.674(2),c=20.409(9)A,β=103.43°(3),V=4946.5A^3,Z=4,最终偏离因子为R=0.051。本文又一次验证了钼(钨)硫成簇反应是分子内部电子转移反应,并提出了可能的成簇反应历程。

Nine new title compounds L_2[M_3O_2S_8][M=Mo, W; L=(n-Bu)_4N, Ph_4P, PyC_(16)H_(33), (CH_3)_3NC_(16)H_(33), Et_4N] were prepared by reaction of [NH_4]_2MOS_3 with LBr and HOAc in methanol, or reaction of [NH_4]_2MoO_2S_2 with LBr in methanol ab t<0℃ and characterazed by elemental analysis, IR, UV spectra and single crystal X-ray diffraction analysis. Cluster crystal data are as follows: [(n-Bu)_4N]_2[Mo_3O_2S_8] (1):Space group P2_(1/c), a=15.910(2), b=15.411(1), c=20.407(5)A, β=103.40 (1)°, V=4867.5 A^2, Z=4. The final R=0.060. [(n-Bu)_4N]_2[W_3O_2S_8] (5): Space group P2_(1/c) a=15.898. (4), b=15.674(2), c=20.409(9)A, β=103.43(3)°, V=4946.5A^3, Z=4. The final R= 0.051. This paper also proposed a mechanism for the formation of clusters.