A lipophilic salt of a transition-metal polyhydride: KOsH3(PMe2Ph)3

John C. Huffman, Mark Green, Susan L. Kaiser, Kenneth G. Caulton

Research output: Contribution to journalArticle

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Abstract

The polyhydride OsH4P3 (P = PMe2Ph) is deprotonated by KH in THF to yield K(fac-OsH3P3), characterized by 1H and 31P NMR spectroscopy. This reaction also proceeds in aromatic solvents, and the ether-free product is soluble in benzene and toluene. Spectral properties in toluene are similar to those in THF but reveal subtle differences. The crystal structure of KOsH3(PMe2Ph)3, crystallized from toluene, reveals the reason for the lipophilic character of this material. It consists of centrosymmetric K2Os2H6(PMe2Ph)6 dimers composed of (PhMe2P)3Os(μ-H)3K monomers (an intimate ion pair) bound into dimers by one additional hydride bridge from each K to one hydride hydrogen in the second monomer unit. Equally important to the dimerization is the enfolding of each K+ by two phenyl rings of the second monomer unit with the result that the periphery of the molecule is entirely hydrocarbon in character. The hard acid/soft base character of the K+/phenyl interaction is particularly surprising. Crystal data for KOsH3(PMe2Ph)3 (at-160°C) are the following: a = 9.990 (2) Å, b = 22.867 (8) Å, c = 12.381 (3) Å, β = 111.44 (1)° with z = 4 in space group P21/n.

Original languageEnglish
Pages (from-to)5111-5115
Number of pages5
JournalJournal of the American Chemical Society
Volume107
Issue number18
StatePublished - 1985

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Toluene
Transition metals
Salts
Monomers
Metals
Hydrides
Dimers
Dimerization
Hydrocarbons
Benzene
Ether
Nuclear magnetic resonance spectroscopy
Hydrogen
Ethers
Magnetic Resonance Spectroscopy
Crystal structure
Ions
Crystals
Molecules
Acids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Huffman, J. C., Green, M., Kaiser, S. L., & Caulton, K. G. (1985). A lipophilic salt of a transition-metal polyhydride: KOsH3(PMe2Ph)3. Journal of the American Chemical Society, 107(18), 5111-5115.

A lipophilic salt of a transition-metal polyhydride : KOsH3(PMe2Ph)3. / Huffman, John C.; Green, Mark; Kaiser, Susan L.; Caulton, Kenneth G.

In: Journal of the American Chemical Society, Vol. 107, No. 18, 1985, p. 5111-5115.

Research output: Contribution to journalArticle

Huffman, JC, Green, M, Kaiser, SL & Caulton, KG 1985, 'A lipophilic salt of a transition-metal polyhydride: KOsH3(PMe2Ph)3', Journal of the American Chemical Society, vol. 107, no. 18, pp. 5111-5115.
Huffman, John C. ; Green, Mark ; Kaiser, Susan L. ; Caulton, Kenneth G. / A lipophilic salt of a transition-metal polyhydride : KOsH3(PMe2Ph)3. In: Journal of the American Chemical Society. 1985 ; Vol. 107, No. 18. pp. 5111-5115.
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abstract = "The polyhydride OsH4P3 (P = PMe2Ph) is deprotonated by KH in THF to yield K(fac-OsH3P3), characterized by 1H and 31P NMR spectroscopy. This reaction also proceeds in aromatic solvents, and the ether-free product is soluble in benzene and toluene. Spectral properties in toluene are similar to those in THF but reveal subtle differences. The crystal structure of KOsH3(PMe2Ph)3, crystallized from toluene, reveals the reason for the lipophilic character of this material. It consists of centrosymmetric K2Os2H6(PMe2Ph)6 dimers composed of (PhMe2P)3Os(μ-H)3K monomers (an intimate ion pair) bound into dimers by one additional hydride bridge from each K to one hydride hydrogen in the second monomer unit. Equally important to the dimerization is the enfolding of each K+ by two phenyl rings of the second monomer unit with the result that the periphery of the molecule is entirely hydrocarbon in character. The hard acid/soft base character of the K+/phenyl interaction is particularly surprising. Crystal data for KOsH3(PMe2Ph)3 (at-160°C) are the following: a = 9.990 (2) {\AA}, b = 22.867 (8) {\AA}, c = 12.381 (3) {\AA}, β = 111.44 (1)° with z = 4 in space group P21/n.",
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N2 - The polyhydride OsH4P3 (P = PMe2Ph) is deprotonated by KH in THF to yield K(fac-OsH3P3), characterized by 1H and 31P NMR spectroscopy. This reaction also proceeds in aromatic solvents, and the ether-free product is soluble in benzene and toluene. Spectral properties in toluene are similar to those in THF but reveal subtle differences. The crystal structure of KOsH3(PMe2Ph)3, crystallized from toluene, reveals the reason for the lipophilic character of this material. It consists of centrosymmetric K2Os2H6(PMe2Ph)6 dimers composed of (PhMe2P)3Os(μ-H)3K monomers (an intimate ion pair) bound into dimers by one additional hydride bridge from each K to one hydride hydrogen in the second monomer unit. Equally important to the dimerization is the enfolding of each K+ by two phenyl rings of the second monomer unit with the result that the periphery of the molecule is entirely hydrocarbon in character. The hard acid/soft base character of the K+/phenyl interaction is particularly surprising. Crystal data for KOsH3(PMe2Ph)3 (at-160°C) are the following: a = 9.990 (2) Å, b = 22.867 (8) Å, c = 12.381 (3) Å, β = 111.44 (1)° with z = 4 in space group P21/n.

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