Nuclear magnetic resonance studies of the solvation of phosphorus(V) selenides, 1,2-bis(diphenylphosphino)ethane, and tris(dimethylamino)phosphine telluride by sulfur dioxide

Abstract

PHILIP A. W. DEAN. Can. J. Chem. 57,754 (1979). 31P and 77Se nmr spectra have been measured for a range of phosphorus(V) selenides, diphosphorus(V) diselenides, and triphosphorus(V) triselenides in the inert solvent CH2C12 and in liquid SO,. Significant roughly-correlated reductions in IIJ(PSe)) and deshielding of the 77Se resonance accompany change of solvent from CH,Cl, to SO,. These changes are shown to arise from 1 : 1 phosphorus(V) selenide:S02 donor:acceptor complex formation. Approximate thermodynamic constants for the formation of the complexes have been determined and possible structures for the 1 : 1 complexes with the diphosphorus(V) diselenides discussed. It is shown from 'H and 31P nmr spectral changes that Ph,P(CH2),PPh2 forms a 1 : 1 complex with SOz, and approximate thermodynamic data for the SO, complexation of the diphosphine have been established. Complexation is indicated by changes in both I1J(PTe) and 6, when (Me2N)3PTe is dissolved in SO,, but the chemical reactivity of this system precluded detailed study.PHILIP A. W. DEAN. Can. J. Chem. 57,754 (1979). On a dttermint les spectres rmn du 31P et du 77Se d'un certain nombre de stltnures de phosphore(V), de distltnures de diphosphore(V) et de triskltnures de triphosphore(V) dans le solvant inerte CH,Cl, et dans le SO, liquide. Un changement de solvent de CH2C12 a SO, s'accompagne de rkductions marqutes qui prtsente une corrklation grossikre des IIJ(PSe)l et des dtblindages de la resonance du 77Se. On a montrt que ces changen~ents sont dus a la formation d'un complexe 1: 1 d0nneur:accepteur stltnure de phosphore(V):S02. On a dttermint les constantes thermodynamiques approximatives pour la formation des complexes et on discute des structures possibles des complexes 1 : 1 avec les distlenures de diphosphore. On a montrt, grace aux chailgements dans les spectres rmn du 'H et du 31P, que le PH2P(CH2)2PPH2 forme un complexe 1 : 1 avec le SO, et on a dttermint les donnkes thermodynamiques approximatives pour la complexation de la diphosphine par le SO,. La complexation est rtvtlte par des changements & la fois dans JIJ(PTe)l et dans le Sp lorsqu'on dissout du (Me2N)3PTe dans le SO,; la rtactivitt chimique de ce systkme ne permet par une ktude plus dttaillke.[Traduit par le journal]

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.…”

“…However, isotopically-enriched PbF, was not available, so PF51AsF5 treatment of Io7Pb-enriched PbO was used to prepare the Io7Pb-enriched hexafluoroarsenate, following the procedure described recently for synthesis of Cd(AsF,), from CdO (4 Nuclear tnogtzeric resonance spectra Broad band proton decoupled 40.45 MHz ,IP nmr spectra were measured using an XL-100-12 spectrometer system and referenced to external OP(OMe), in (CD,),CO as reported earlier (10); the 8 mm sample tubes were held coaxially in 12 mm precision nmr tubes using a Teflon spacer. All lI9Sn spectra were measured with a Bruker WH-400 spectrometer system operating at 148.93 without IH decoupling.…”

Rhodium(I) carbonyl complexes of mono selenium functionalized bis(diphenylphosphino)methane and bis(diphenylphosphino)amine chelating ligands and their catalytic carbonylation activity

“…Metal complexes of functionalized phosphines particularly potential chelating ligands like phosphine-phosphine monochalcogenides with different backbones have attracted much attention in the recent time because of their structural novelty, reactivity and catalytic activity [1][2][3][4][5][6][7][8][9][10][11][12]. Presence of two different types of donor sites makes the chemistry of these ligands more fascinating as they can coordinate to the metal center in bidentate or monodentate way [13,14].…”

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

“…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 …”

“…A 32 K Fourier transform was performed. Conditions for measurement of 3 1 P spectra have been given before (17).…”