A DYNAMIC NMR-STUDY OF 1,2-METALLOTROPIC SHIFTS IN TRIMETHYLPLATINUM(IV) HALIDE-COMPLEXES OF 3-METHYLPYRIDAZINE
A DYNAMIC NMR-STUDY OF 1,2-METALLOTROPIC SHIFTS IN TRIMETHYLPLATINUM(IV) HALIDE-COMPLEXES OF 3-METHYLPYRIDAZINE
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DOI：
10.1016/s0277-5387(00)86624-3
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发表时间：
1994-10-01
期刊：
影响因子：
2.6
通讯作者：
SIK, V
中科院分区：
文献类型：
--
作者：
ABEL, EW;HEARD, PJ;SIK, V
3-甲基吡嗪（3- mepydz）与卤代三甲基铂（IV） [(PtXMe(3))(4)]反应生成fac-[PtXMe(3)(3- mepydz)(2)] （X = Cl， Br或I）型配合物。在溶液中，这些配合物在相邻的氮供体之间发生1,2-金相转移，产生不同的连锁异构体。这些异构体的溶液丰度受到3-甲基在吡啶环上的空间效应的强烈影响，(1,1)-异构体总是占主导地位（类似于95%）。通过变温H-1核磁共振谱法确定了该流体的活化能，（1,1）—>(1,2)异构体位移的值在74-78 kJ mol（-1）之间。
3-Methylpyridazine (3-Mepydz) reacts with halogenotrimethylplatinum(IV), [(PtXMe(3))(4)], to afford complexes of type fac-[PtXMe(3)(3-Mepydz)(2)] (X = Cl, Br or I). In solution these complexes undergo 1,2-metallotropic shifts between the contiguous nitrogen donors producing different linkage isomers. Solution abundances of these isomers are strongly influenced by the steric effects of the 3-methyl group on the pyridazine ring, with the (1,1)-isomer always being predominant (similar to 95%). Activation energies for the fluxion were determined by variable temperature H-1 NMR spectroscopy, values of the (1,1) --> (1,2) isomer shift being in the range 74-78 kJ mol(-1).