The preparation and NMR characterization of a hydrido-bridged gold-iridium binuclear complex containing the chelating tritertiary phosphine ligand Cyttp

Steven M. Socol; Devon W. Meek; Robert Glaser

doi:10.1016/S0277-5387(00)86412-8

The preparation and NMR characterization of a hydrido-bridged gold-iridium binuclear complex containing the chelating tritertiary phosphine ligand Cyttp

Steven M. Socol, Devon W. Meek, Robert Glaser

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Apical(H,Cl)-anti-mer-{IrHCl(Cyttp)(μ-H)[AuPPh₃]}BF₄, where Cyttp = C₆H₅P(CH₂CH₂CH₂P(C₆H₁₁)₂)₂, was prepared in THF solution by mixing equimolar quantities of cis-anti-mer-[IrH₂Cl(Cyttp)] and [AuCl(PPh₃)] in the presence of TlBF₄. The ¹H NMR spectrum (acetone-d₆) showed resonances of an apical terminal hydrido proton at -19.68 ppm and a meridional bridging hydrido proton at -5.45 ppm. The assignment of meridional stereochemistry to the bridging hydride indicates that the [Au(THF)PPh₃]⁺ cation attacked the diastereotopic proton that was located trans to the higher trans-influence ligand in the starting complex. Nuclear Overhauser Effect experiments confirm the apical assignment for the terminal hydride and show that it is spatially close to the ortho-protons of the phenyl group (i.e. an anti-configuration diastereomer in which phenyl and chlorine are located on opposite sides of the meridional reference place). Geminal heteronuclear ²J_AuP-(μ-H) coupling constants for the spin-spin interactions between the μ-hydrido proton and the Cyttp internal phosphorus atom (65.9(3) Hz) or the phosphorus atom bonded to gold (71.1(3) Hz) indicate trans linear-type PIr(μ-H) and (μ-H)AuP relationships.

Original language	English
Pages (from-to)	1903-1908
Number of pages	6
Journal	Polyhedron
Volume	8
Issue number	15
DOIs	https://doi.org/10.1016/S0277-5387(00)86412-8
State	Published - 1 Jan 1989

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0277-5387(00)86412-8

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title = "The preparation and NMR characterization of a hydrido-bridged gold-iridium binuclear complex containing the chelating tritertiary phosphine ligand Cyttp",

abstract = "Apical(H,Cl)-anti-mer-{IrHCl(Cyttp)(μ-H)[AuPPh3]}BF4, where Cyttp = C6H5P(CH2CH2CH2P(C6H11)2)2, was prepared in THF solution by mixing equimolar quantities of cis-anti-mer-[IrH2Cl(Cyttp)] and [AuCl(PPh3)] in the presence of TlBF4. The 1H NMR spectrum (acetone-d6) showed resonances of an apical terminal hydrido proton at -19.68 ppm and a meridional bridging hydrido proton at -5.45 ppm. The assignment of meridional stereochemistry to the bridging hydride indicates that the [Au(THF)PPh3]+ cation attacked the diastereotopic proton that was located trans to the higher trans-influence ligand in the starting complex. Nuclear Overhauser Effect experiments confirm the apical assignment for the terminal hydride and show that it is spatially close to the ortho-protons of the phenyl group (i.e. an anti-configuration diastereomer in which phenyl and chlorine are located on opposite sides of the meridional reference place). Geminal heteronuclear 2JAuP-(μ-H) coupling constants for the spin-spin interactions between the μ-hydrido proton and the Cyttp internal phosphorus atom (65.9(3) Hz) or the phosphorus atom bonded to gold (71.1(3) Hz) indicate trans linear-type PIr(μ-H) and (μ-H)AuP relationships.",

author = "Socol, {Steven M.} and Meek, {Devon W.} and Robert Glaser",

year = "1989",

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doi = "10.1016/S0277-5387(00)86412-8",

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T1 - The preparation and NMR characterization of a hydrido-bridged gold-iridium binuclear complex containing the chelating tritertiary phosphine ligand Cyttp

AU - Socol, Steven M.

AU - Meek, Devon W.

AU - Glaser, Robert

PY - 1989/1/1

Y1 - 1989/1/1

N2 - Apical(H,Cl)-anti-mer-{IrHCl(Cyttp)(μ-H)[AuPPh3]}BF4, where Cyttp = C6H5P(CH2CH2CH2P(C6H11)2)2, was prepared in THF solution by mixing equimolar quantities of cis-anti-mer-[IrH2Cl(Cyttp)] and [AuCl(PPh3)] in the presence of TlBF4. The 1H NMR spectrum (acetone-d6) showed resonances of an apical terminal hydrido proton at -19.68 ppm and a meridional bridging hydrido proton at -5.45 ppm. The assignment of meridional stereochemistry to the bridging hydride indicates that the [Au(THF)PPh3]+ cation attacked the diastereotopic proton that was located trans to the higher trans-influence ligand in the starting complex. Nuclear Overhauser Effect experiments confirm the apical assignment for the terminal hydride and show that it is spatially close to the ortho-protons of the phenyl group (i.e. an anti-configuration diastereomer in which phenyl and chlorine are located on opposite sides of the meridional reference place). Geminal heteronuclear 2JAuP-(μ-H) coupling constants for the spin-spin interactions between the μ-hydrido proton and the Cyttp internal phosphorus atom (65.9(3) Hz) or the phosphorus atom bonded to gold (71.1(3) Hz) indicate trans linear-type PIr(μ-H) and (μ-H)AuP relationships.

AB - Apical(H,Cl)-anti-mer-{IrHCl(Cyttp)(μ-H)[AuPPh3]}BF4, where Cyttp = C6H5P(CH2CH2CH2P(C6H11)2)2, was prepared in THF solution by mixing equimolar quantities of cis-anti-mer-[IrH2Cl(Cyttp)] and [AuCl(PPh3)] in the presence of TlBF4. The 1H NMR spectrum (acetone-d6) showed resonances of an apical terminal hydrido proton at -19.68 ppm and a meridional bridging hydrido proton at -5.45 ppm. The assignment of meridional stereochemistry to the bridging hydride indicates that the [Au(THF)PPh3]+ cation attacked the diastereotopic proton that was located trans to the higher trans-influence ligand in the starting complex. Nuclear Overhauser Effect experiments confirm the apical assignment for the terminal hydride and show that it is spatially close to the ortho-protons of the phenyl group (i.e. an anti-configuration diastereomer in which phenyl and chlorine are located on opposite sides of the meridional reference place). Geminal heteronuclear 2JAuP-(μ-H) coupling constants for the spin-spin interactions between the μ-hydrido proton and the Cyttp internal phosphorus atom (65.9(3) Hz) or the phosphorus atom bonded to gold (71.1(3) Hz) indicate trans linear-type PIr(μ-H) and (μ-H)AuP relationships.

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U2 - 10.1016/S0277-5387(00)86412-8

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JO - Polyhedron

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ER -

The preparation and NMR characterization of a hydrido-bridged gold-iridium binuclear complex containing the chelating tritertiary phosphine ligand Cyttp

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