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18767076

Source:http://linkedlifedata.com/resource/pubmed/id/18767076

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pubmed-article:18767076rdf:typepubmed:Citationlld:pubmed
pubmed-article:18767076lifeskim:mentionsumls-concept:C0443286lld:lifeskim
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pubmed-article:18767076pubmed:issue30lld:pubmed
pubmed-article:18767076pubmed:dateCreated2008-10-16lld:pubmed
pubmed-article:18767076pubmed:abstractTextThe reaction of the 16e half-sandwich complex [CpCo(S2C2B10H10)] (1S; Cp: cyclopentadienyl) with ethynylferrocene in CH2Cl2 at ambient temperature leads to [CpCo(S2C2B10H9)-(CH2CFc)] (2S; Fc: ferrocenyl) and 1,2,4-triferrocenylbenzene. In 2S, B substitution occurs at the carborane cage in the position B3/B6 with the formation of a C-B bond. In the presence of the protic solvent MeOH, 2S loses a CpCo fragment to generate [(CH2CFc)(S2C2B10H9)] (3S). On the other hand, 2S can take a free CpCo fragment to form [(CpCo)2(S2C2B9H8)-(CHCFc)] (4S) containing a nido-C2B9 unit. In sharp contrast, [CpCo-(Se2C2B10H10)] (1Se) does not react with the alkyne in CH2Cl2, but in MeOH [(CHCFc)(Se2C2B10H10)] (5Se) is generated without the presence of a CpCo unit. The reaction of 1 with dimethyl acetylenedicarboxylate at ambient temperature leads to insertion compounds [CpCo(E2C2B10H10){(MeO2C)-C=C(CO2Me)}] (6S, E=S; 6 Se, E=Se). Upon heating, 6S rearranges to two geometrical isomers [CpCo(S2C2B10H9){(MeO2C)C=CH(CO2Me)}] (7S) and [CpCo(S2C2B10H9){(MeO2C)-CHC(CO2Me)}] (8S). In both, B-H functionalization takes place at the carborane cage in the position B3/B6, but 7S is a 16e complex with an olefinic unit in a Z configuration, and 8S is an 18e complex containing an alkyl B-CH group. Further treatment of 7 S with dimethyl acetylenedicarboxylate at ambient temperature affords two B-disubstituted complexes at the carborane cage in the positions of the B3 and B6 sites, that is, [CpCo(S2C2-B10H8){(MeO2C)C=CH(CO2Me)}2] (9S) and [CpCo(S2C2B10H8){(MeO2C)-CHC(CO2Me)}{(MeO2C)C=CH-(CO2Me)}] (10S). Compound 9S is a 16e complex with two olefinic units in E/E configurations, whereas 10S is an 18e species containing both an olefinic substituent and an alkyl B--CH unit. The reaction of 7S with methyl acetylenemonocarboxylate at ambient temperature leads to the sole 16e compound [CpCo(S2C2B10H8){CH=CH(CO2Me)}-{(MeO2C)C=CH(CO2Me)}] (11S). In contrast, 6Se does not rearrange. All new complexes 2S-4S, 5Se, 6Se, and 7S-11S were characterized by NMR spectroscopy (1H, 11B, 13C) and X-ray structural analyses were performed for 2S-4S, 5Se, 6Se, and 7S-9S.lld:pubmed
pubmed-article:18767076pubmed:languageenglld:pubmed
pubmed-article:18767076pubmed:journalhttp://linkedlifedata.com/r...lld:pubmed
pubmed-article:18767076pubmed:statusPubMed-not-MEDLINElld:pubmed
pubmed-article:18767076pubmed:issn0947-6539lld:pubmed
pubmed-article:18767076pubmed:authorpubmed-author:YanHongHlld:pubmed
pubmed-article:18767076pubmed:authorpubmed-author:LiYi-ZhiYZlld:pubmed
pubmed-article:18767076pubmed:authorpubmed-author:XuBao-HuaBHlld:pubmed
pubmed-article:18767076pubmed:authorpubmed-author:PengXu-QingXQlld:pubmed
pubmed-article:18767076pubmed:issnTypePrintlld:pubmed
pubmed-article:18767076pubmed:volume14lld:pubmed
pubmed-article:18767076pubmed:ownerNLMlld:pubmed
pubmed-article:18767076pubmed:authorsCompleteYlld:pubmed
pubmed-article:18767076pubmed:pagination9347-56lld:pubmed
pubmed-article:18767076pubmed:dateRevised2009-8-4lld:pubmed
pubmed-article:18767076pubmed:year2008lld:pubmed
pubmed-article:18767076pubmed:articleTitleReactions of 16e CpCo half-sandwich complexes containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligand with ethynylferrocene and dimethyl acetylenedicarboxylate.lld:pubmed
pubmed-article:18767076pubmed:affiliationState Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University-Jin Chuan Group Ltd., Nanjing, Jiangsu 210093, China.lld:pubmed
pubmed-article:18767076pubmed:publicationTypeJournal Articlelld:pubmed