Show simple item record

dc.contributor.authorHan, Feifeizh_CN
dc.contributor.authorWang, Tongdaozh_CN
dc.contributor.authorLi, Jinhuazh_CN
dc.contributor.authorZhang, Hongzh_CN
dc.contributor.authorXia, Haipingzh_CN
dc.contributor.author张弘zh_CN
dc.contributor.author夏海平zh_CN
dc.date.accessioned2015-07-22T03:21:17Z
dc.date.available2015-07-22T03:21:17Z
dc.date.issued2014-04-07zh_CN
dc.identifier.citationCHEMISTRY-A EUROPEAN JOURNAL, 2014,20(15):4363-4372zh_CN
dc.identifier.otherWOS:000333632800023zh_CN
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/89329
dc.description973 Program [2012CB821600]; National Natural Science Foundation of China [21174115, 21272193, 21332002]; Natural Science Foundation of Fujian Province [2011J05031]zh_CN
dc.description.abstractTreatment of the osmium complex [Os{CHC-(PPh3)CH(OH)-(2)-CCH}(PPh3)(2)(NCS)(2)] (1) with excess triethylamine produces the first m-metallaphenol complex [Os{CHC(PPh3)CHC(OH)CH}(PPh3)(2)(NCS)(2)] (2). The NMR spectroscopic and structural data as well as the nucleus-independent chemical-shift (NICS) values suggest that osmaphenol 2 has aromatic character. The reactivity studies demonstrate that 2 can react with different isocyanates to form the annulation reaction products [Os{CHC(PPh3)CHC(OCONR)C}(PPh3)(2)(NCS)(2)] (R=Ph (3), iPr (7), Bn (8)) via the carbamate intermediates [Os{CHC(PPh3)CHC(O-CONHR)CH}(PPh3)(2)(NCS)(2)] (R=Ph (4), iPr (5), Bn (6)). In addition, the similar annulation reactions can be extended to other unsaturated compounds containing N-C multiple bonds, for example, isothiocyanates, pyridine, and sodium thiocyanate, which can produce the corresponding fused osmabenzene complexes. In contrast, the reactions of 2 with common electrophiles, such as NOBF4, NO2BF4, N-bromosuccinimide, and N-chlorosuccinimide only led to the decomposition of the metallaphenol ring. The experimental results suggest that 2 is very electrophilic and readily reacts with nucleophiles, which is mainly due to the metal center and the strong electron-withdrawing phosphonium group.zh_CN
dc.language.isoen_USzh_CN
dc.publisherWILEY-V C H VERLAG GMBHzh_CN
dc.source.urihttp://dx.doi.org/10.1002/chem.201304957zh_CN
dc.subjectELECTROPHILIC SUBSTITUTION-REACTIONSzh_CN
dc.subjectNUCLEOPHILIC AROMATIC-SUBSTITUTIONzh_CN
dc.subjectCRYSTAL-STRUCTUREzh_CN
dc.subjectTRANSITION-METALzh_CN
dc.subjectMETALLABENZENESzh_CN
dc.subjectCHEMISTRYzh_CN
dc.subjectCOMPLEXzh_CN
dc.subjectOSMABENZENEzh_CN
dc.subjectDENSITYzh_CN
dc.subjectMETALLACYCLESzh_CN
dc.titlem-Metallaphenol: Synthesis and Reactivity Studieszh_CN
dc.typeArticlezh_CN


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record