A ³¹P nuclear magnetic resonance spectroscopic study of some 2:1,3:1, and 4:1 complexes of phosphine sulfides and selenides with cadmium(II), including some complexes with mixed ligands

Abstract

Using low-temperature 31P nmr, many new complexes formed between divalent cadmium (as Cd(SbF6)2) and monodentate phosphine chalcogenides in liquid SO2 have been characterized. A 4:1 (L:M) complex is formed with Bu′3PS and, possibly, Bu′3PSe. 4:1 and 3:1 complexes are formed with Ph3PE, (o-C6H4Me)Ph2PE, (p-C6H4Me)3PE, and (C6H11)3PE (E = S or Se) as well as (o-C6H4Me)2PhPSe, while 4:1, 3:1 and 2:1 complexes occur for (o-C6H4Me)3PE (E = S or Se), and, probably, (o-C6H4Me)2PhPS. In addition, ail the mixed ligand complexes in the series [Cd(SeP(C6H11)3)n(SP(C6H11)3)4–n]2+, [Cd(SeP(C6H11)3)n(SP(C6H11)3)3–n]2+, and [Cd(SeP(o-C6H4Me)3)n(SP(o-C6H4Me)3)3–n]2+ have been identified.Trends in the 31P nmr data are discussed.

The phosphorus-31 and metal nuclear magnetic resonance spectra of complexes of tin(II) and lead(II) with tricyclohexylphosphine oxide, sulfide, and selenide

“…The literature routes to Sn(SbF,), (9), and Pb(SbF,), and Pb(AsF,),.xSO, (I) were used to prepare metal salts without isotopic enrichment. Tricyclohexylphosphine oxide, sulfide, and selenide were prepared during earlier work (3,4,10). Sulfur dioxide (Canadian Liquid Air Ltd., Anhydrous Grade) was stored in the gas phase over Linde 3A Molecular Sieves for at least 12h before use.…”

A 113Cd nuclear magnetic resonance study of some complexes of cadmium with phosphine oxides, sulfides, and selenides

“…Our intention was to establish a series of related complexes of Group VIA donor ligands in which the kernel could be varied methodically, so providing a basis for a "'Cd nmr study in which the effect of systematic change about the cadmium could be investigated. There is general agreement on the need for more and better model compound studies to advance the plexes we characterized earlier (1,2). Unambiguous slow exchange l13Cd spectra have been observed, allowing us to assess the effect on the " T d resonance of change of donor atom only, change in ligation number only, change of substituents on the phosphorus atom of the phosphine chalcogenides, and change in the number and size of chelate rings in six-coordinate complexes of chelating phosphine oxides.…”

“…We have previously suggested. from the variation of 2J(111/113-Cd-E-P) with the number of ligands coordinated, that solventlanion involvement is slight (2). At the same time it must be recognized that Sa % -230ppm for Cd(AsF6), or Cd(SbF6), in SO2 (16), so replacement of EPR, (E = S or Se) by S02/AsF6-might well lead to extensive shielding of the cadmium resonance.…”

“…double distillation in a nitrogen atmosphere. The literature routes (16) to Cd(AsF,), and Cd(SbF,), were used to prepare the In this paper we present "3Cd Ilmr for salts containing ";Cd in natural abundance, and the preparaselected members from among the cadmium corn-tions of the ligands, except OP(C,H,,),, have been given earlier also (1,2,17 …”

“…Previously, we have used reduced temperature 31P nmr to characterize, in SO, solution, a wide range of cadmium complexes with phosphine oxides, sulfides, or selenides, as well as some mixtures of these, as ligands (1,2). Our intention was to establish a series of related complexes of Group VIA donor ligands in which the kernel could be varied methodically, so providing a basis for a "'Cd nmr study in which the effect of systematic change about the cadmium could be investigated.…”