cis-[Pt(depe)(NCS)(SCN)]和cis-[Pt(dPr^ipe)(NCS)]配合物的合成和分子结构  

Syntheses and Molecular Structures of cis-Pt(dPr^ipe) (NCS)_2 and cis-Pt (depe) (NCS) (SCN) Complexes

作　　者：姜琼忠 张良辅[1] 李广年[1] 周忠远[2] 胡国志[2] 郁开北[2] 

机构地区：[1]中国科学院成都有机化学研究所 [2]中国科学院成都分析测试中心

出　　处：《化学学报》1990年第8期778-783,共6页Acta Chimica Sinica

基　　金：国家自然科学基金

摘　　要：本文研究了在1∶1丙酮-水混合溶剂中,回流条件下,cis-[Pt(diphos)Cl_2]与NaCNS之间的取代反应,第一次合成了CNS-的混合键合异构体的depe铂配合物cis-[Pt(depe)(NCS)(SCN)],进行了分子结构测定,属单斜晶系,空间群为P2_(1/n),晶胞参数:a=7.296(5),b=14.434(4),c=18.042(4) ,β=95.72(8)°,V=1890.7 ~3,Z=4,R_F=0.0564.在相同条件下用dPr^ipe作了对照实验,得到的是cis-[Pt(dPr^ipe)(NCS)_2],属单斜晶系,空间群为Cc,晶胞参数:a=12.279(6),b=9.330(8),c=20.102(7) ,β=108.90(9)°,V=2179.0(3) ~3,Z=4,R_F=0.0419。此外,还从双膦烷基的空间效应和电子效应讨论了对取代反应产物的影响。The syntheses and crystal structure determinations of the title complexes were reported. The cis-Pt (dPr^ipe) (NCS)_2 complex [dPr^ipe is 1, 2-bis (diisopropylphosphino) ethane] forms monoclinic crystal with unit cell dimensions of a=12.279(6), b=9.330 (8), c=20.102 (7) , with β=108.90(9)° and spaoe group Cc. The cis-Pt (depe) (NCS) (SCN) complex [depe is 1, 2-his (diethylphosphino)-ethano] forms monoclinic crystal of space group P2_(1/n) with cell dimensions of a=7.296 (5), b=14.434 (4) and c=18.042 (4) , and β=95.72(8)°. The structures were solved by the heavy-atom method and refined by least-squares techniques to unweighted R values of 0.0419 for complex containing dPr^ipe and 0.0564 for complex containing depe. In these complexes, the most important observation is that the thio cyanato coordination changes from N, S bonded form for depe to N, N bonded for dPr^ipe. This linkage isomerization is explained in terms of storic effects.

关 键 词：铂配合物 NS混合键合 异构配体 

分 类 号：O614.826[理学—无机化学]