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

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

doi:10.1016/S0022-328X(02)01368-2

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 journal › Article › peer-review

23 Scopus citations

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.

Original language	English (US)
Pages (from-to)	124-131
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	651
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(02)01368-2
State	Published - May 15 2002
Externally published	Yes

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

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10.1016/S0022-328X(02)01368-2

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@article{117b80ef38b943b8b0b495dd117269aa,

title = "CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster",

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.",

keywords = "Benzyne, Cluster, Cyclomerallation, Ortho-metallation, P-C cleavage, Ruthenium",

author = "Adams, {Richard D.} and Burjor Captain and Wei Fu and Smith, {Mark D.}",

note = "Funding Information: We thank the Office of Basic Energy Sciences of the US Department of Energy for financial support. ",

year = "2002",

month = may,

day = "15",

doi = "10.1016/S0022-328X(02)01368-2",

language = "English (US)",

volume = "651",

pages = "124--131",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

T1 - CH and PC bond activations of PMe2Ph ligands by an octahedral Ru6 cluster

AU - Adams, Richard D.

AU - Captain, Burjor

AU - Fu, Wei

AU - Smith, Mark D.

N1 - Funding Information: We thank the Office of Basic Energy Sciences of the US Department of Energy for financial support.

PY - 2002/5/15

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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U2 - 10.1016/S0022-328X(02)01368-2

DO - 10.1016/S0022-328X(02)01368-2

M3 - Article

AN - SCOPUS:0037093154

VL - 651

SP - 124

EP - 131

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -