Dialkylaminofluorophosphine complexes of rhodium(I)

M. A. Bennett, T. W. Turney

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3 Citations (Scopus)

Abstract

Diethylaminodifluorophosphine, PF2NEt2, forms dimeric, halogen-bridged rhodium(I) complexes [RhX(PF2NEt2)2]2 (X = Cl or I) which react reversibly with an excess of the ligand to give non-ionic, five-coordinate complexes RhX(PF2NEt2)4. Dimethylaminodifluorophosphine, PF2NMe2, forms analogous complexes but, in contrast with diethylaminodifluorophosphine, the complex RhCL(PF2NMe2)4 decomposes thermally to give initially an isolable tris complex RhCl(PF2NMe2)4 which has no known counterpart in CO or PF3 chemistry. The tris-complex decomposes thermally to give [RhCl(PF2NMe2)2]2. Bis(dimethylamino)fluorophosphine, PF(NMe2)2 forms a tris complex, RhCl PF(NMe2)23, but a dimeric bis-ligand complex could not be isolated. In contrast with tertiary phosphines and phosphites, the fluorophosphines do not form ionic rhodium(I) species. Monomeric derivatives such as Rh(acac)(PF2NEt2)2, Rh(C5H5)(PF2NEt2)2, RhCl(PF2NEt2)(PPh3)2 and RhCl(PPh3)(PF2NEt2)2 have been prepared. The complexes [RhCl(CO)2]2 and [RhCl(PF2NEt2)2] undergo ligand redistribution on mixing, the product consisting mainly of [RhCl(CO)(PF2NEt2)]2. 19F n.m.r, data are reported and used inter alia to show that Rh(acac)(PF2NEt2)2, but not Rh(C5H5)(PF2NEt2)2, exchanges rapidly with free PF2NEt2, and that, in RhCl(PPh3)(PF2NEt2)2, the fluorophosphine ligands are mutually cis. Bands in the infrared arising from P-F vibrations are reported and discussed. The dialkylaminofluorophosphines appear to be poorer π-acceptors and/or better σ-donors than PF3, but are better π-acceptors than phosphites.

Original languageEnglish
Pages (from-to)2335-2348
Number of pages14
JournalAustralian Journal of Chemistry
Volume26
Issue number11
DOIs
Publication statusPublished - 1 Jan 1973
Externally publishedYes

Cite this

@article{dcdfbb342f8948da97400be7ab84cdfd,
title = "Dialkylaminofluorophosphine complexes of rhodium(I)",
abstract = "Diethylaminodifluorophosphine, PF2NEt2, forms dimeric, halogen-bridged rhodium(I) complexes [RhX(PF2NEt2)2]2 (X = Cl or I) which react reversibly with an excess of the ligand to give non-ionic, five-coordinate complexes RhX(PF2NEt2)4. Dimethylaminodifluorophosphine, PF2NMe2, forms analogous complexes but, in contrast with diethylaminodifluorophosphine, the complex RhCL(PF2NMe2)4 decomposes thermally to give initially an isolable tris complex RhCl(PF2NMe2)4 which has no known counterpart in CO or PF3 chemistry. The tris-complex decomposes thermally to give [RhCl(PF2NMe2)2]2. Bis(dimethylamino)fluorophosphine, PF(NMe2)2 forms a tris complex, RhCl PF(NMe2)23, but a dimeric bis-ligand complex could not be isolated. In contrast with tertiary phosphines and phosphites, the fluorophosphines do not form ionic rhodium(I) species. Monomeric derivatives such as Rh(acac)(PF2NEt2)2, Rh(C5H5)(PF2NEt2)2, RhCl(PF2NEt2)(PPh3)2 and RhCl(PPh3)(PF2NEt2)2 have been prepared. The complexes [RhCl(CO)2]2 and [RhCl(PF2NEt2)2] undergo ligand redistribution on mixing, the product consisting mainly of [RhCl(CO)(PF2NEt2)]2. 19F n.m.r, data are reported and used inter alia to show that Rh(acac)(PF2NEt2)2, but not Rh(C5H5)(PF2NEt2)2, exchanges rapidly with free PF2NEt2, and that, in RhCl(PPh3)(PF2NEt2)2, the fluorophosphine ligands are mutually cis. Bands in the infrared arising from P-F vibrations are reported and discussed. The dialkylaminofluorophosphines appear to be poorer π-acceptors and/or better σ-donors than PF3, but are better π-acceptors than phosphites.",
author = "Bennett, {M. A.} and Turney, {T. W.}",
year = "1973",
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Dialkylaminofluorophosphine complexes of rhodium(I). / Bennett, M. A.; Turney, T. W.

In: Australian Journal of Chemistry, Vol. 26, No. 11, 01.01.1973, p. 2335-2348.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Dialkylaminofluorophosphine complexes of rhodium(I)

AU - Bennett, M. A.

AU - Turney, T. W.

PY - 1973/1/1

Y1 - 1973/1/1

N2 - Diethylaminodifluorophosphine, PF2NEt2, forms dimeric, halogen-bridged rhodium(I) complexes [RhX(PF2NEt2)2]2 (X = Cl or I) which react reversibly with an excess of the ligand to give non-ionic, five-coordinate complexes RhX(PF2NEt2)4. Dimethylaminodifluorophosphine, PF2NMe2, forms analogous complexes but, in contrast with diethylaminodifluorophosphine, the complex RhCL(PF2NMe2)4 decomposes thermally to give initially an isolable tris complex RhCl(PF2NMe2)4 which has no known counterpart in CO or PF3 chemistry. The tris-complex decomposes thermally to give [RhCl(PF2NMe2)2]2. Bis(dimethylamino)fluorophosphine, PF(NMe2)2 forms a tris complex, RhCl PF(NMe2)23, but a dimeric bis-ligand complex could not be isolated. In contrast with tertiary phosphines and phosphites, the fluorophosphines do not form ionic rhodium(I) species. Monomeric derivatives such as Rh(acac)(PF2NEt2)2, Rh(C5H5)(PF2NEt2)2, RhCl(PF2NEt2)(PPh3)2 and RhCl(PPh3)(PF2NEt2)2 have been prepared. The complexes [RhCl(CO)2]2 and [RhCl(PF2NEt2)2] undergo ligand redistribution on mixing, the product consisting mainly of [RhCl(CO)(PF2NEt2)]2. 19F n.m.r, data are reported and used inter alia to show that Rh(acac)(PF2NEt2)2, but not Rh(C5H5)(PF2NEt2)2, exchanges rapidly with free PF2NEt2, and that, in RhCl(PPh3)(PF2NEt2)2, the fluorophosphine ligands are mutually cis. Bands in the infrared arising from P-F vibrations are reported and discussed. The dialkylaminofluorophosphines appear to be poorer π-acceptors and/or better σ-donors than PF3, but are better π-acceptors than phosphites.

AB - Diethylaminodifluorophosphine, PF2NEt2, forms dimeric, halogen-bridged rhodium(I) complexes [RhX(PF2NEt2)2]2 (X = Cl or I) which react reversibly with an excess of the ligand to give non-ionic, five-coordinate complexes RhX(PF2NEt2)4. Dimethylaminodifluorophosphine, PF2NMe2, forms analogous complexes but, in contrast with diethylaminodifluorophosphine, the complex RhCL(PF2NMe2)4 decomposes thermally to give initially an isolable tris complex RhCl(PF2NMe2)4 which has no known counterpart in CO or PF3 chemistry. The tris-complex decomposes thermally to give [RhCl(PF2NMe2)2]2. Bis(dimethylamino)fluorophosphine, PF(NMe2)2 forms a tris complex, RhCl PF(NMe2)23, but a dimeric bis-ligand complex could not be isolated. In contrast with tertiary phosphines and phosphites, the fluorophosphines do not form ionic rhodium(I) species. Monomeric derivatives such as Rh(acac)(PF2NEt2)2, Rh(C5H5)(PF2NEt2)2, RhCl(PF2NEt2)(PPh3)2 and RhCl(PPh3)(PF2NEt2)2 have been prepared. The complexes [RhCl(CO)2]2 and [RhCl(PF2NEt2)2] undergo ligand redistribution on mixing, the product consisting mainly of [RhCl(CO)(PF2NEt2)]2. 19F n.m.r, data are reported and used inter alia to show that Rh(acac)(PF2NEt2)2, but not Rh(C5H5)(PF2NEt2)2, exchanges rapidly with free PF2NEt2, and that, in RhCl(PPh3)(PF2NEt2)2, the fluorophosphine ligands are mutually cis. Bands in the infrared arising from P-F vibrations are reported and discussed. The dialkylaminofluorophosphines appear to be poorer π-acceptors and/or better σ-donors than PF3, but are better π-acceptors than phosphites.

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U2 - 10.1071/CH9732335

DO - 10.1071/CH9732335

M3 - Article

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