含烯烃配体的过渡金属卡宾配合物的研究 ⅩⅥ.丁二烯-和异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物与三苯膦和亚磷酸三苯酯的反应研究  

Studies on Olefin-Coordinating Transition Metal Carbene Complexes ⅩⅥ. Studies on The Reactions of Isomerized Products of Butadiene-and Isoprene (dicarbonyl) [ethoxy (aryl) carbene] iron Complexes with Triphenyl Phosphine and Triphenyl Phosphite

作　　者：王天兰[1] 陈家碧[1] 王绮文[1] 

机构地区：[1]中国科学院上海有机化学研究所,上海200032

出　　处：《化学学报》1991年第3期265-271,共7页Acta Chimica Sinica

基　　金：中国科学院科学基金;国家自然科学基金

摘　　要：丁二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物,C_4H_6(CO)_2FeC(OC_2H_5)Ar(1,Ar=苯基,2,Ar=对甲苯基),在己烷溶液中于-60到-40℃与三苯膦或亚磷酸三苯酯反应生成产物3-6.当1与三苯膦在己烷中于60—70℃反应时,除了生成3外,还获得双膦配位的产物7.而异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物与亚磷酸三苯酯反应则生成橙黄色结晶产物9,9的X射线衍射研究表明,二烯配体的键型发生了有趣的变化,即原铁配合物的π-烯丙基部分变为更有趣的含芳环的三烯体系和生成一个η~4配体以满足18电子规则.The reaction of isomerized product of butadiene (dicarbonyl) [ethoxy(aryl)-carbene] iron complex, C_4H_6(CO)_2FeC(OC_2H_5)Ar(1, Ar=phenyl and 2, Ar=p-tolyl) with triphenyl phosphine and triphenyl phosphite gave products 3, 4 and 5, 6, respectively at-60 to-30℃. When 1 was reacted with triphenyl phosphine in hexane at 60 to 70℃, in addition to 3, a diphsphine coordinated product 7 was also obtained. While the isomerized isoprene (dicarbonyl) [ethoxy(aryl)carbene] iron complex reacted with triphenyl phosphite to give an orange-yellow crystalline compound 9. The X-ray diffraction study of 9 showed that an interesting change of the bonding of the diene ligand took plaoe, namely, the original π-allyl moiety of the iron complex was changed to a more profound conjugated triene system including the aromatic ring and formed a η~4 ligand, in order to satisfy the 18 electronic rule.

关 键 词：烯烃配体 过渡金属 卡宾配合物 

分 类 号：O641.4[理学—物理化学]