[（η^5—C5Me5）WS3Cu3Br2（PPyPh2）2]四核簇合物的合成和晶体结构

Synthesis and Crystal Structure of a Tetranuclear Cluster [(η5-C5Me5)WS3Cu3Br2(PPyPh2)2]

以 [PPh4 ]2 [(η5-C5Me5) WS3(Cu Br) 3]2 和 diphenyl-2 -pyridylphosphine(PPy Ph2 )在乙腈中反应得到标题化合物 [(η5-C5Me5) WS3Cu3Br2 (PPy Ph2 ) 2 ],对该产物进行了元素分析、IR、UV-Vis和 1 H NMR谱表征 ,并测定了晶体结构 .该化合物晶体属三斜晶系 ,P1空间群 ,晶胞参数 :a=1 .5 45 9(7) nm,b=1 .62 0 (1 )nm,c=1 .0 1 80 (2 ) nm,α=94.1 8(3 )°,β=97.3 8(3 )°,γ=1 1 1 .81 (4 )°,V=2 .3 2 7(2 ) nm3,Z=2 ,Dc=1 .84g· cm- 3,F(0 0 0 ) =1 2 60 ,μ=5 7.77cm- 1 ,最终偏离因子 R=0 .0 2 9.此簇合物结构可视为由一个 [(η5-C5Me5) WS3]单元和 3个 Cu组成的开口立方烷 ,其中 2个 Cu是畸变四面体配位 ,第 3个 Cu是近似三角平面配位 .W— Cu(1 ) ,W— Cu(2 )和 W—Cu(3 )距离分别为 0 .2 70 41 (9) ,0 .2 73 2 7(8) ,0 .2 6785 (9) nm.

Reaction of \\-2\[(\%η\%\+5\|C\-5Me\-5)WS\-3(CuBr)\-3\]\-2 in CH\-3CN with PPyPh\-2 in a molar ratio of \{1∶4\} gave rise to red crystals of \[(\%η\%\+5\|C\-5Me\-5)WS\-3Cu\-3Br\-2(PPyPh\-2)\-2\]. It was characterized by elemental analysis, IR, UV\|Vis and \{\}\+1H NMR spectroscopy and X\|ray diffraction. It crystallizes in a triclinic system with space group \%P\%1 and unit cell parameters \%a\%=1.545 9(7) nm, \%b\%=1.62 0(1) nm, \%c\%=\{1.018 0(2) nm\}, \%α=94.18(3)°, β=97.38(3)°, γ\%=111.8(4)°, \%Z=2, R\%=0.031. The structure consists of a distorted WS\-3Cu\-3Br cubane where the Cu(3)\_Br(1) bond is broken. Cu(1) and Cu(2) atoms adopt a distorted tetrahedral geometry coordination while Cu(3) assumes an approximately trigonal planar geometry. W\_Cu(1), W\_Cu(2) and W\_Cu(3) distances are 0.270 41(9), 0.273 27(8), and 0.267 85(9) nm, respectively.