多晶二烷基二硫代磷酸铜（I）簇合物的固态³¹P交叉极化/魔角旋转和静态⁶⁵Cu核磁共振表征

Solid-state 31P CP/MAS and static 65Cu NMR characterization of polycrystalline copper(I) dialkyldithiophosphate clusters.

作者信息

Rusanova Daniela, Forsling Willis, Antzutkin Oleg N, Pike Kevin J, Dupree Ray

机构信息

Luleå University of Technology, Division of Chemistry, SE 971 87 Luleå, Sweden.

出版信息

J Magn Reson. 2006 Mar;179(1):140-5. doi: 10.1016/j.jmr.2005.10.013. Epub 2005 Nov 17.

DOI:10.1016/j.jmr.2005.10.013

PMID:16298533

Abstract

Polycrystalline tetra-nuclear Cu4[S2P(O-i-C3H7)2]4, hexa-nuclear Cu6[S2P(OC2H5)2]6, and octa-nuclear Cu8[S2P(O-i-C4H9)2]6(S) complexes were synthesized and analyzed by means of solid-state 31P CP/MAS and 65Cu static NMR spectroscopy. The symmetries of the electronic environments around each P-site were estimated from the 31P chemical shift anisotropy (CSA) parameters, Deltaaniso and eta. The 65Cu chemical shift and quadrupolar splitting parameters obtained from the experimental 65Cu NMR spectra of the polycrystalline Cu(I)-complexes are presented. A solid-state NMR approach for the elucidation of the stereochemistry of poly-nuclear Cu(I) dithiophosphate complexes, when the structural analysis of the systems by single-crystal X-ray diffraction is not readily available, is proposed.

摘要

合成了多晶四核Cu4[S2P(O-i-C3H7)2]4、六核Cu6[S2P(OC2H5)2]6和八核Cu8[S2P(O-i-C4H9)2]6(S)络合物，并通过固态31P CP/MAS和65Cu静态核磁共振光谱进行了分析。根据31P化学位移各向异性（CSA）参数Deltaaniso和eta估算了每个P位点周围电子环境的对称性。给出了从多晶Cu(I)络合物的实验65Cu NMR光谱获得的65Cu化学位移和四极分裂参数。提出了一种在无法通过单晶X射线衍射对体系进行结构分析时，用于阐明多核Cu(I)二硫代磷酸酯络合物立体化学的固态NMR方法。