DC Field | Value | Language |
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dc.contributor.author | Song, Hyunjoon | - |
dc.contributor.author | Lee, Chang H. | - |
dc.contributor.author | Lee, Kwangyeol | - |
dc.contributor.author | Park, Joon T. | - |
dc.date.accessioned | 2010-12-07 | - |
dc.date.available | 2010-12-07 | - |
dc.date.issued | 2002 | - |
dc.identifier.citation | Organometallics, Vol.21, pp.2514-2520 | en |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.uri | http://hdl.handle.net/10203/20783 | - |
dc.description.abstract | The reaction of Os3(CO)9(μ3-η2:η2:η2-C60) (1) with PhCH2NPPh3 in chlorobenzene affords the benzyl isocyanide substituted product Os3(CO)8(CNR)(μ3-η2:η2:η2-C60) (2a, R = CH2Ph) in 76% yield. Photolysis of 1 in the presence of an excess of benzyl isocyanide gives the isocyanide-inserted product Os3(CO)9(μ3-CNR)(μ3-η1:η2:η1-C60) (2b) in 11% yield. Thermal reaction of 2a with an excess of RNC in chlorobenzene at 80 °C produces two isocyanide-inserted, isomeric products, Os3(CO)8(CNR)(μ3-CNR)(μ3-η1:η2:η1-C60) (3a, 22%; 3b, 27%). The two isomers 3a and 3b can be selectively prepared by photolysis of 2a in the presence of excess isocyanide in 49% yield and by decarbonylation of 2b with Me3NO/MeCN and subsequent reaction with isocyanide in 56% yield, respectively. Compounds 2a,b and 3a,b have been characterized by microanalytical and spectroscopic methods. In particular, the sp3 carbons of M−C(C60) σ-interactions in μ3-η1:η2:η1-C60 complexes exhibit unique upfield resonances around 39 ppm in the 13C NMR spectra, compared to the π-bonded sp3 carbon resonances observed in the range of 95−65 ppm. The X-ray crystallographic studies for 2a,b and 3a,b reveal that μ3-η2:η2:η2-C60 ligands in 1 and 2a transform into new σ-type μ3-η1:η2:η1-C60 ligands in 2b and 3a,b by insertion of the isocyanide ligand concomitant with Os−Os bond cleavage, forming a bent triosmium framework. In compounds 2b and 3b, a boat-shaped 1,4-cyclohexadiene-like C6 ring in the C60 molecule is clearly observed and the M−C60 σ-bond distances (average 2.24 Å) are shorter than the π-bond lengths (average 2.41 Å). This study represents a novel ligand-induced conversion of π to σ C60−metal complexes. | en |
dc.description.sponsorship | This work was supported by the National Research Laboratory (NRL) Program of Korean Ministry of Science & Technology (MOST) and the Korea Science Engineering Foundation (Project No. 1999-1-122-001-5). | en |
dc.language.iso | en_US | en |
dc.publisher | American Chemical Society | en |
dc.title | Ligand-Induced Conversion of pi to sigma C60-Metal Cluster Complexes; Full Characterization of the mu3-eta1;eta2;eta1-C60 Bonding Mode | en |
dc.type | Article | en |
dc.identifier.doi | 10.1021/om020109a | - |
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