三烷基膦－铂－氢配合物的合成及NMR研究

Synthesis and NMR Studies of Trialkyl Phosphine Platinum(Ⅱ)-Hydrogen Complexes

合成了配合物ｔｒａｎｓ－ＰｔＨＸＬ２（Ｌ＝ＰＢｕ３、ＰＰｒ３、Ｐｅｔ３；Ｘ＝Ｃｌ－、Ｂｒ－、Ｉ－、ＳＣＮ－、ＣＮ－），并进行了１ＨＮＭＲ研究。测得Ｐｔ－Ｈ键的１Ｈ在高场的化学位移δＨ＝－８～－２４ｐｐｍ；１Ｊ（Ｐｔ－Ｈ）＝８００～１５００Ｈｚ和２Ｊ（Ｐ－Ｈ）＝１３．０～１７．０Ｈｚ。鉴定了配合物的顺反异构和键合异构。研究了阴离子配体（Ｘ）及中性配体（Ｌ）对Ｐｔ－Ｈ键的δＨ、１Ｊ（Ｐｔ－Ｈ）及２Ｊ（Ｐ－Ｈ）的影响，Ｐｔ－Ｈ键长与Ｐｔ－ＨδＨ的关系。Ｐｔ－Ｈ化学位移与Ｐｔ－Ｈ的伸展振动频率呈线性关系。

Trans-PtHXL2 complexes containing anionic ligands(X)and neutral ligands(L)(L=PBu3,PPr3,PEt3)were synthesized.1H NMR spectra of these complexes were determined.Structure of these complexes and the linkage isomers of trans-PtHSC-NL2 complexes were identified.1H NMR spectra of complexes obtained show a very large high-field Pt-H chemical shift(δH)in the range of-8～-24ppm,Pt-H coupling constants(1JPt-H)are also large,and range 800～1500Hz,2JP-H=13.0～17.0Hz.The effects of ligands(X),(L)on the Pt-H chemieal shift(δH)and coupling constants,as well as the effect of the length of Pt-H bond on the Pt-H chemical shift(δH)were studied.Linear relationship between the Pt-H chemical shift(δH)and Pt-H stretch vibration frequency(vpt-H)were obtained.