CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster

Richard D. Adams, Burjor Captain, Wei Fu, Mark D. Smith

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

The compound solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO·2H2O to yield two new products Ru6(CO)13(μ-PMe2)(μ33-Me2PC6H4)(μ6-C) (2) and Ru6(CO)14(PMe2Ph)(μ-η2-MePhPCH2)(μ6-C)(μ-H) (3). Compound 2 is also obtained from 1 by thermal decarbonylation at 127 °C together with two additional compounds: Ru6(CO)14(μ-PMe2)(μ-η2-MePhPCH2) (μ6-C) (4) and Ru6(CO)12(μ-PMe2)232-C6H4)(μ6-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru6(CO)14 (μ-ηPMe2)(μ-η2-Me2PC6H4)(μ6-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral Ru 6 clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging η3-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging η2-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging η2-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (μ32-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging η2-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands.

Original languageEnglish
Pages (from-to)124-131
Number of pages8
JournalJournal of Organometallic Chemistry
Volume651
Issue number1-2
DOIs
StatePublished - May 15 2002
Externally publishedYes

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Chemical activation
Ligands
activation
methylidyne
ligands
phosphine
rings
phosphines
Isomers
adducts
cleavage
isomers
Hot Temperature
degradation
Degradation

Keywords

  • Benzyne
  • Cluster
  • Cyclomerallation
  • Ortho-metallation
  • P-C cleavage
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster. / Adams, Richard D.; Captain, Burjor; Fu, Wei; Smith, Mark D.

In: Journal of Organometallic Chemistry, Vol. 651, No. 1-2, 15.05.2002, p. 124-131.

Research output: Contribution to journalArticle

Adams, Richard D. ; Captain, Burjor ; Fu, Wei ; Smith, Mark D. / CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster. In: Journal of Organometallic Chemistry. 2002 ; Vol. 651, No. 1-2. pp. 124-131.
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abstract = "The compound solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO·2H2O to yield two new products Ru6(CO)13(μ-PMe2)(μ3-η3-Me2PC6H4)(μ6-C) (2) and Ru6(CO)14(PMe2Ph)(μ-η2-MePhPCH2)(μ6-C)(μ-H) (3). Compound 2 is also obtained from 1 by thermal decarbonylation at 127 °C together with two additional compounds: Ru6(CO)14(μ-PMe2)(μ-η2-MePhPCH2) (μ6-C) (4) and Ru6(CO)12(μ-PMe2)2(μ3-η2-C6H4)(μ6-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru6(CO)14 (μ-ηPMe2)(μ-η2-Me2PC6H4)(μ6-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral Ru 6 clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging η3-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging η2-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging η2-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (μ3-η2-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging η2-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands.",
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AU - Captain, Burjor

AU - Fu, Wei

AU - Smith, Mark D.

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Y1 - 2002/5/15

N2 - The compound solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO·2H2O to yield two new products Ru6(CO)13(μ-PMe2)(μ3-η3-Me2PC6H4)(μ6-C) (2) and Ru6(CO)14(PMe2Ph)(μ-η2-MePhPCH2)(μ6-C)(μ-H) (3). Compound 2 is also obtained from 1 by thermal decarbonylation at 127 °C together with two additional compounds: Ru6(CO)14(μ-PMe2)(μ-η2-MePhPCH2) (μ6-C) (4) and Ru6(CO)12(μ-PMe2)2(μ3-η2-C6H4)(μ6-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru6(CO)14 (μ-ηPMe2)(μ-η2-Me2PC6H4)(μ6-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral Ru 6 clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging η3-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging η2-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging η2-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (μ3-η2-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging η2-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands.

AB - The compound solution as a mixture of two slowly interconverting isomers. It is decarbonylated by treatment with Me3NO·2H2O to yield two new products Ru6(CO)13(μ-PMe2)(μ3-η3-Me2PC6H4)(μ6-C) (2) and Ru6(CO)14(PMe2Ph)(μ-η2-MePhPCH2)(μ6-C)(μ-H) (3). Compound 2 is also obtained from 1 by thermal decarbonylation at 127 °C together with two additional compounds: Ru6(CO)14(μ-PMe2)(μ-η2-MePhPCH2) (μ6-C) (4) and Ru6(CO)12(μ-PMe2)2(μ3-η2-C6H4)(μ6-C) (5). Compound 2 reacts reversibly with CO to form the CO adduct Ru6(CO)14 (μ-ηPMe2)(μ-η2-Me2PC6H4)(μ6-C) (6). The structures of compounds 1-6 were established crystallographically. All contain octahedral Ru 6 clusters with a carbido ligand in the center. Except for 1, all contain phosphine ligands in various stages of degradation. Compound 2 contains one bridging PMe2 ligand formed by loss of a phenyl ring from a PMe2Ph ligand and a bridging η3-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of the second PMe2Ph ligand. Compound 3 contains a bridging η2-MePhPCH2 ligand formed by metallation of one of the methyl groups of a PMe2Ph ligand. Compound 4 contains a bridging PMe2 and a bridging η2-MePhPCH2 ligand. Compound 5 contains two bridging PMe2 ligands and a bridging (μ3-η2-C6H4) benzyne ligand fromed by cleavage of a phenyl ring from one of the PMe2Ph ligands. Compound 6 contains one bridging PMe2 ligand and a bridging η2-Me2PC6H4 ligand formed by ortho-metallation of the phenyl ring of one of the PMe2Ph ligands.

KW - Benzyne

KW - Cluster

KW - Cyclomerallation

KW - Ortho-metallation

KW - P-C cleavage

KW - Ruthenium

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