Reactions of halogenohydridobis(triethylphosphine)platinum(II) with trihalogenophosphines: some unusual complexes of Pt II containing five-co-ordinated phosphorus
作者:Christopher W. Allen、E. A. V. Ebsworth、Steven G. Henderson、David W. H. Rankin、Heather E. Robertson、Bryan Turner、John D. Whitelock
DOI:10.1039/dt9860001333
日期:——
at 180 K to give [PtCl2H2(PEt3)2], (5), and the previously unknown [PtCl(PEt3)2(P′Cl2)], (4). On warming to 240 K, complex (5) decomposes and (4) is reversibly protonated to give [PtCl(PEt3)2(P′Cl2H)]+. Above 240 K, (4) is converted into the novel [PtCl(PEt3)2(P′Cl2H2)], (8). This complex is stable in solution up to 260 K, but decomposes irreversibly at higher temperatures. Changes in the n.m.r. spectra
31 P Nmr光谱显示[PtClH(PEt 3) 2 ]在180 K下与CH 2 Cl 2中的PCl 3反应生成[PtCl 2 H 2(PEt 3) 2 ],( 5)和先前未知的[PtCl (PEt 3) 2(P'Cl 2)],( 4)。升温至240 K时,复合物( 5)分解,并且( 4)可逆地质子化,得到[PtCl(PEt 3) 2(P'Cl 2 H)] +。240 K以上,( 4)转换为新颖的[PtCl(PEt 3)2(P'Cl 2 H 2)],(8)。该配合物在高达260 K的溶液中稳定,但在较高温度下不可逆地分解。根据(8)分解为[PtCl (PEt 3)2(P'ClH 2)] +和[HCl 2 ] –或[BCl 4 ] –的解离,可以解释添加HCl或BCl 3时nmr光谱的变化。[PtBrH(PEt 3)2 ]与PBr 3在160 K下反应得到[PtBr2 H(PEt 3) 2(P'Br