Mono- and polynuclear transition-metal complexes of the linear, small-bite tris(phosphine) bis((diphenylphosphino)methyl)phenylphosphine

Alan L. Balch, Rosalvina R. Guimerans, John Linehan

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Abstract

Bis((diphenylphosphino)methyl)phenylphosphine (dpmp) forms chelated complexes Pt(dpmp)(CH3)2, Pt(dpmp)(CN)2, Pd(dpmp)X2 (X = Cl, Br, I) and M(dpmp)(CO)4 (M = Cr, Mo, W) in which the internal phosphorus atom is uncoordinated. Spectroscopic characterization by 31P and 1H NMR and infrared is reported. In solution, Pd(dpmp)X2 (X = Cl, Br) reacts with itself to form PdX2(μ-dpmp)Pd(dpmp)X]X, which has been identified by 31P NMR spectroscopy. These chelated monomers react with other d8 metal ions to form trinuclear complexes: trans-Rh(CO)Cl[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PtCl2, PdCl2, Mo(CO)4; cis-PtCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4; trans-PdCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4. NMR spectroscopic properties indicative of the formation of these trinuclear complexes include a downfield shift of the 31P resonance of the internal phosphorus atom of dpmp, a reduction of J(P,P) from 60-80 Hz in the bidentate chelates to less than 5 Hz in the dpmp-bridged complexes, and increased complexity in the upheld methylene resonance in the 1H NMR spectrum. The metal centers appear to be remote from one another and noninteracting in these trinuclear complexes.

Original languageEnglish
Pages (from-to)290-296
Number of pages7
JournalInorganic Chemistry
Volume24
Issue number3
Publication statusPublished - 1985

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phosphine
Coordination Complexes
Carbon Monoxide
phosphines
Transition metals
transition metals
nuclear magnetic resonance
Nuclear magnetic resonance
phosphorus
Phosphorus
Atoms
chelates
methylene
atoms
metal ions
monomers
Nuclear magnetic resonance spectroscopy
Metal ions
Monomers
Metals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Mono- and polynuclear transition-metal complexes of the linear, small-bite tris(phosphine) bis((diphenylphosphino)methyl)phenylphosphine. / Balch, Alan L.; Guimerans, Rosalvina R.; Linehan, John.

In: Inorganic Chemistry, Vol. 24, No. 3, 1985, p. 290-296.

Research output: Contribution to journalArticle

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abstract = "Bis((diphenylphosphino)methyl)phenylphosphine (dpmp) forms chelated complexes Pt(dpmp)(CH3)2, Pt(dpmp)(CN)2, Pd(dpmp)X2 (X = Cl, Br, I) and M(dpmp)(CO)4 (M = Cr, Mo, W) in which the internal phosphorus atom is uncoordinated. Spectroscopic characterization by 31P and 1H NMR and infrared is reported. In solution, Pd(dpmp)X2 (X = Cl, Br) reacts with itself to form PdX2(μ-dpmp)Pd(dpmp)X]X, which has been identified by 31P NMR spectroscopy. These chelated monomers react with other d8 metal ions to form trinuclear complexes: trans-Rh(CO)Cl[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PtCl2, PdCl2, Mo(CO)4; cis-PtCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4; trans-PdCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4. NMR spectroscopic properties indicative of the formation of these trinuclear complexes include a downfield shift of the 31P resonance of the internal phosphorus atom of dpmp, a reduction of J(P,P) from 60-80 Hz in the bidentate chelates to less than 5 Hz in the dpmp-bridged complexes, and increased complexity in the upheld methylene resonance in the 1H NMR spectrum. The metal centers appear to be remote from one another and noninteracting in these trinuclear complexes.",
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T1 - Mono- and polynuclear transition-metal complexes of the linear, small-bite tris(phosphine) bis((diphenylphosphino)methyl)phenylphosphine

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N2 - Bis((diphenylphosphino)methyl)phenylphosphine (dpmp) forms chelated complexes Pt(dpmp)(CH3)2, Pt(dpmp)(CN)2, Pd(dpmp)X2 (X = Cl, Br, I) and M(dpmp)(CO)4 (M = Cr, Mo, W) in which the internal phosphorus atom is uncoordinated. Spectroscopic characterization by 31P and 1H NMR and infrared is reported. In solution, Pd(dpmp)X2 (X = Cl, Br) reacts with itself to form PdX2(μ-dpmp)Pd(dpmp)X]X, which has been identified by 31P NMR spectroscopy. These chelated monomers react with other d8 metal ions to form trinuclear complexes: trans-Rh(CO)Cl[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PtCl2, PdCl2, Mo(CO)4; cis-PtCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4; trans-PdCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4. NMR spectroscopic properties indicative of the formation of these trinuclear complexes include a downfield shift of the 31P resonance of the internal phosphorus atom of dpmp, a reduction of J(P,P) from 60-80 Hz in the bidentate chelates to less than 5 Hz in the dpmp-bridged complexes, and increased complexity in the upheld methylene resonance in the 1H NMR spectrum. The metal centers appear to be remote from one another and noninteracting in these trinuclear complexes.

AB - Bis((diphenylphosphino)methyl)phenylphosphine (dpmp) forms chelated complexes Pt(dpmp)(CH3)2, Pt(dpmp)(CN)2, Pd(dpmp)X2 (X = Cl, Br, I) and M(dpmp)(CO)4 (M = Cr, Mo, W) in which the internal phosphorus atom is uncoordinated. Spectroscopic characterization by 31P and 1H NMR and infrared is reported. In solution, Pd(dpmp)X2 (X = Cl, Br) reacts with itself to form PdX2(μ-dpmp)Pd(dpmp)X]X, which has been identified by 31P NMR spectroscopy. These chelated monomers react with other d8 metal ions to form trinuclear complexes: trans-Rh(CO)Cl[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PtCl2, PdCl2, Mo(CO)4; cis-PtCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4; trans-PdCl2[(μ-dpmp)MLn]2, MLn = Pt(CH3)2, PdCl2, Mo(CO)4. NMR spectroscopic properties indicative of the formation of these trinuclear complexes include a downfield shift of the 31P resonance of the internal phosphorus atom of dpmp, a reduction of J(P,P) from 60-80 Hz in the bidentate chelates to less than 5 Hz in the dpmp-bridged complexes, and increased complexity in the upheld methylene resonance in the 1H NMR spectrum. The metal centers appear to be remote from one another and noninteracting in these trinuclear complexes.

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