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dc.contributor.author杨玉
dc.contributor.author蔡涛
dc.contributor.author温庭斌
dc.date.accessioned2018-11-26T07:26:57Z
dc.date.available2018-11-26T07:26:57Z
dc.date.issued2017-06
dc.identifier.citation有机化学,2017,(1):176-184
dc.identifier.issn0253-2786
dc.identifier.other10.6023/cjoc201608013
dc.identifier.urihttps://dspace.xmu.edu.cn/handle/2288/162905
dc.description.abstract简单的锇起始物OsHCl(PPh_3)_3(1)或OsCl_2(PPh_3)_3(2)与3-氯-3-甲基-1-丁炔反应可分别得到锇的烯基卡拜配合; 物OsHCl_2(=CCH=CMe_2)(PPh_3)_2(3)和OsCl_3(=CCH=CMe_2)(PPh_3)_2(4).化合物3与二苯基; (苯乙炔基)膦反应可转化为三个二苯基(苯乙炔基)膦配位的锇烯基卡宾配合物OsCl_2(=CHCH=CMe_2)(Ph_2PC=CPh)_3(5); ,而化合物4与二苯基(苯乙炔基)膦反应得到膦配体取代产物OsCl_3(=CCH=CMe_2)(Ph_2PC=CPh)_2(6).二苯基(苯乙炔基; )膦配体较弱的供电子能力及较小的空间位阻是促成化合物3发生锇上的原子氢配体到卡拜碳的1,2-迁移而转化为卡宾配合物5的原因.
dc.description.abstractReactions of the simple osmium precursors OsHCl(PPh3)(3) (1) or OsCl2(PPh3)(3) (2) with 3-chloro-3-methylbut-1-yne afforded OsHCl2( CCH=CMe2)(PPh3)(2) (3) or OsCl3( CCH=CMe2)(PPh3)(2) (4), respectively. Treatment of 3 with Ph2PC CPh led to alp formation of the tris-diphenyl(phenylethynyl)phosphine alkenylcarbene complex OsCl2(=CHCH=CMe2)(Ph2PC CPh)(3) (5), while complex 4 underwent simple phosphine ligand substitution with Ph2PC CPh to give OsCl3( CCH=CMe2)(Ph2PC-CPh)(2) (6). Presumably, upon the phosphine ligand substitution of PPh3 in 3 by Ph2PC CPh, the relatively electron -poor nature of the later decreased the electron density of the osmium center, and thus promoted the transformation of the hydride-carbyne to carbene via the 1,2 -shift of the hydride ligand from Os to the carbyne carbon, which was then further facilitated by the coordination of a third less bulky Ph2PC-CPh ligand to the osmium center to give the stable 18e product 5.
dc.description.sponsorshipNational Basic Research Prpgram of China (973 Program) [2012CB821600];; National Natural Science Foundation of China [21072161]
dc.language.isozh_CN
dc.subjectCarbene
dc.subjectCarbyne
dc.subjectDiphenyl(phenylethynyl)phosphine
dc.subjectOsmium
dc.subjectPropargyl chloride
dc.subjectosmium
dc.subjectcarbyne
dc.subjectcarbene
dc.subjectdiphenyl(phenylethynyl)phosphine
dc.subjectpropargyl
dc.subjectchloride
dc.titleOsXCl(PPh_3)_3 (X=H, Cl)与炔丙基氯反应合成烯基卡拜配合物及膦配体调控的锇-氢卡拜向卡宾配合物的转化
dc.title.alternativeAlkenylcarbyne Complexes Derived from the Reactions of OsXCl-(PPh3)(3) (X=H, Cl) with Propargyl Chloride and Phosphine Ligand-Controlled Transformation of Hydride-Carbyne to Carbene
dc.typeArticle


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