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 |
|---|---|
| Pages (from-to) | 124-131 |
| Number of pages | 8 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 651 |
| Issue number | 1-2 |
| DOIs | |
| State | Published - May 15 2002 |
| Externally published | Yes |
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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 journal › Article
}
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.
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
UR - http://www.scopus.com/inward/record.url?scp=0037093154&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0037093154&partnerID=8YFLogxK
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 -