金属核的磁共振研究*Ⅱ含磷配体铂(Ⅱ)络合物的195Pt和31P-NMR谱

本文测定了12个含苯基环戊基磷、亚磷酸、卤素等配体的铂(Ⅱ)络合物的¹⁹⁵Pt、³¹P-NMR谱,考察了溶剂、浓度、温度对¹⁹⁵Pt谱的影响,研究了¹⁹⁵Pt、³¹P化学位移、偶合常数与络合物几何构型的关系及对卤素的依赖关系。讨论1,2-丙二胺溶液中络合物³¹P谱的变化,以及各种含亚磷酸配体的铂络合物¹⁹⁵Pt和³¹P谱的变化。

THE NMR STUDY OF METALLIC NUCLEI Ⅱ THE 195Pt AND 31P NMR SPECTRA OF PHOSPHORUS CONTAINING PLATINUM (Ⅱ) COMPLEXES

The ¹⁹⁵Pt, ³¹P-NMR spectra were recorded for 12 platinum(Ⅱ) complexes containing phenyl cyclopentyl phosphine, phosphite and halogen ligands The influence of solvent,concentration and temperature on the ¹⁹⁵Pt spectra were investigated Lewis base solvents cause ¹⁹⁵Pt resonances moving upfield. For cis-Pt(PPh₃)₂Cl₂ in CH₂Cl₂ solution, ¹⁹⁵Pt concentration coefficient is -17.8ppm/mol, and temperature coefficient is 0. 43ppm/℃. It was found that the ¹⁹⁵Pt, ³¹P chemical shifts of cis-isomers are less than those of trans-isomers, δ_cis < δ_trans, and coupling constants of cis-isomers are greater than those of trans-isomers, (¹Jp_t-P)_cis > (¹Jp_t-p)_trans. Normal halogen dependence was observed for the complexes cis-Pt(PPh₃)₂X₂, the order of δ(¹⁹⁵Pt), δ(³¹P), 1Jpt-p values is Cl > Br > I. In 1, 2-diaminopropane solution the ¹⁹⁵Pt satellite of ³¹P spectrum is the AB part of ABX system, whereas the central peak appears as a singlet.The ₁₉₅Pt, ³¹P spectra of phosphite platinum complexes were also discussed.