Jacobsen Faith E, Breece Robert M, Myers William K, Tierney David L, Cohen Seth M
Department of Chemistry and Biochemistry, University of California-San Diego, La Jolla, CA 92093-0358, USA.
Inorg Chem. 2006 Sep 4;45(18):7306-15. doi: 10.1021/ic060901u.
The tetrahedral cobalt(II) complex [(Tp(Ph,Me))CoCl] (Tp(Ph,Me) = hydrotris(3,5-phenylmethylpyrazolyl)borate) was combined with several hydroxypyridinone, hydroxypyridinethione, pyrone, and thiopyrone ligands to form the corresponding [(Tp(Ph,Me))Co(L)] complexes. X-ray crystal structures of these complexes were obtained to determine the mode of binding for each ligand L. The structures show that the [(Tp(Ph,Me))Co(L)] complexes are pentacoordinate complexes, with a general tendency toward square pyramidal geometry. The electronic, EPR, and paramagnetic NMR spectroscopy of the [(Tp(Ph,Me))Co(L)] complexes have been examined. The frozen-solution EPR spectra are indicative of pentacoordination in frozen solution, while the NMR indicates some dynamics in ligand binding. The findings presented here suggest that [(Tp(Ph,Me))Co(L)] complexes can be used as spectroscopic references for investigating the mode of inhibitor binding in metalloproteinases of medicinal interest. Potential limitations when using cobalt(II) model complexes are also discussed.
四面体钴（II）配合物[(Tp(Ph,Me))CoCl]（Tp(Ph,Me) = 氢三（3,5 - 苯基甲基吡唑基）硼酸酯）与几种羟基吡啶酮、羟基吡啶硫酮、吡喃酮和硫代吡喃酮配体结合，形成相应的[(Tp(Ph,Me))Co(L)]配合物。获得了这些配合物的X射线晶体结构，以确定每个配体L的结合模式。结构表明，[(Tp(Ph,Me))Co(L)]配合物是五配位配合物，总体上倾向于四方锥几何构型。对[(Tp(Ph,Me))Co(L)]配合物的电子、电子顺磁共振和顺磁核磁共振光谱进行了研究。冷冻溶液的电子顺磁共振光谱表明在冷冻溶液中存在五配位，而核磁共振表明配体结合存在一些动力学。此处呈现的研究结果表明，[(Tp(Ph,Me))Co(L)]配合物可作为光谱参考，用于研究具有药用价值的金属蛋白酶中抑制剂的结合模式。还讨论了使用钴（II）模型配合物时的潜在局限性。
