OsXCl(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  

Alkenylcarbyne Complexes Derived from the Reactions of OsXCl(PPh_3)_3(X=H, Cl) with Propargyl Chloride and Phosphine Ligand-Controlled Transformation of Hydride-Carbyne to Carbene

作　　者：杨玉[1] 蔡涛[1] 温庭斌[1] 

机构地区：[1]厦门大学化学化工学院化学系,厦门361005

出　　处：《有机化学》2017年第1期176-184,共9页Chinese Journal of Organic Chemistry

基　　金：国家重点基础研究发展计划(973计划;No.2012CB821600);国家自然科学基金(No.21072161)资助项目~~

摘　　要：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.Reactions 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 Ph_2PC≡CPh led to the formation of the tris-diphenyl（phenylethynyl）phosphine alkenylcarbene complex OsCl_2（=CHCH=CMe2）（Ph2PC≡CPh）3（5）,while complex 4 underwent simple phosphine ligand substitution with Ph2PC≡CPh to give OsCl3（≡CCH=CMe_2）（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 18 e product 5.

关 键 词：锇 卡拜 卡宾 二苯基(苯乙炔基)膦 炔丙基氯 

分 类 号：O641.4[理学—物理化学]