trans-PtHx(AsPh_3)_2配合物的合成及核磁共振研究

Synthesis and NMR Studies of Triphenyl Arsine Platinum(Ⅱ)-Hydrogen Complexes

合成了 trans-PtHX(AsPh_3)_2(X=Cl^-、Br^-、I^-、SCN^-)四个配合物,除 trars-PtHCl(AsPh_3)_2外,其余三个为新配合物。用 NMR 和 IR 谱鉴定了结构和 trans-PtHSCN(AsPh_3)_2 的键合异构。研究了配体(X)对铂-氢化学位移(δ_H)和铂-氢偶合常数(J_(Pt-H))的影响、铂-氢键键长与铂-氢化学位移(δ_H)的关系以及铂-氢化学位移(δ_H)与铂-氢伸展振动频率的相关性。发现 trans-PtHCl(AsPh_3)_2 在不同溶剂中的重结晶产物,其 Pt-H 键的红外伸展振动频率不同,而 ~1HNMR 谱(在 CDCl_3 中)完全一样。

Four trans-PtHX(AsPh_3)_2(X=Cl^-,Br^-,I^-,SCN^-)complexes were synthesized.Except trans-PtHCl(AsPh_3)_2 complexes,others are new complexes.Structure of these complexes and linkage isomers of trans-PtSCN(AsPh+3)_2 were identified by ~1H- NMR and IR spectra.The effects of anionic ligands(X)on the Pt-H chemical shift and coupling constants,as well as the effect of the length of Pt-H bond on Pt-H chemical shift were studied.Linear relationships between Pt-H chemical shift(δ_(Pt-H_)and Pt-H stretch vibration frequency(K-a)were obtained.