MULTINUCLEAR (P-31, PT-195) MAGNETIC-RESONANCE AND ELECTROSPRAY MASS-SPECTROMETRIC STUDIES OF THE REACTIONS BETWEEN PLATINUM BIS(DITHIOLATES) AND 2 POTENTIALLY TETRADENTATE PHOSPHINE-LIGANDS

被引：20

作者：

COLTON, R ^{[1
]}

TRAEGER, JC ^{[1
]}

TEDESCO, V ^{[1
]}

机构：

[1] UNIV MELBOURNE,SCH CHEM,INORGAN CHEM SECT,PARKVILLE,VIC 3052,AUSTRALIA

来源：

INORGANICA CHIMICA ACTA | 1993年 / 210卷 / 02期

基金：

澳大利亚研究理事会;

关键词：

D O I：

10.1016/S0020-1693(00)83327-7

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of platinum(II) bis(dithiolates) Pt(S-S)2 ((S-S) = S2P(OEt)2 (dtp), S2COnPr (xan), S2CNEt2 (dtc)) with two potentially tetradentate phosphine ligands have been investigated by multinuclear magnetic resonance spectroscopy and electrospray mass spectrometry (ESMS). The phosphines used were P(CH2CH2PPh2)3 (P3P') and Ph2PCH2CH2P(Ph)CH2CH2P(Ph)CH2CH2PPh2 (P2P'2). P-31 and Pt-195 NMR spectroscopies show that P3P' reacts in dichloromethane solution with Pt(dtp)2 and Pt(xan), to give five-coordinate [(eta4-P3P')Pt(eta1-S-S)]+ and with Pt(dtc), to give a temperature dependent mixture of [(eta4-P3P')Pt(eta1-dtc)]+ and [(eta3-P3P')Pt(eta2-dtc)]+. All these formulations were confirmed by observation of the intact ions in the ES mass spectra directly from the solutions. [(eta4-P3P')Pt(eta1-xan)]+ slowly reacts with the free xan ion to give the dithiocarbonate complex (eta3-P3P')Pt(eta2-S2CO). The pendant phosphine in [eta3-P3P')Pt(eta2-dtc]+ undergoes various chemical reactions such as methylation and reaction with sulfur, and the cation behaves as a monodentate phosphine towards Pt(dtp)2 to give [(eta1-dtp)(eta2-dtp)Pt(eta1-mu2-eta3-P3P')Pt(eta2-dtc)]+ which was fully characterised by multi-NMR spectroscopy and confirmed by observation of the intact ion by ESMS. P2P'2 reacts with Pt(dtp)2 to give [(P2P'2)Pt]2+, but with Pt(xan)2 and Pt(dtc)2 the products are [(eta4-P2P'2)Pt(eta1-S-S)]+, but the xanthate complex slowly de-alkylates to give (eta3-P2P'2)Pt(eta2-S2CO). The identities of the cationic P2P'2 species in solution were confirmed by direct observation of the intact ion by ESMS.

引用

页码：193 / 201

页数：9

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