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

丁二烯二羰基乙氧基(芳基)卡宾]铁配合物的异构化产物,C4H6(CO)2FeC(OC2H5)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产产物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。

Studies on olefin-coordineting transition metal carbene complexes XVI. Studies on the reactions of isomerized products of butaduene and isoprene (dicarbonyl)[ethoxy(aryl) carbene] iron complexes with triphenyl phosphine and triphenyl phosphite

The reaction of isomerized butadiene(dicarbonyl)ethoxy(aryl)carbene]iron complex (I; R = Ph, p-tolyl) with triphenylphosphine and tri-Ph phosphite gave products II (same R; R1 = Ph, OPh), at -60 to -30? When I (R = Ph) was reacted with triphenylphosphine in hexane at 60 to 70?in addition to II (R = R1 = Ph), a diphosphine coordinated product III was also obtained. Isomerized isoprene(dicarbonyl)ethoxy(aryl)carbene]iron complex reacted with tri-Ph phosphite to give an orange-yellow crystalline compound IV. The x-ray diffraction study of IV showed that an interesting change of the bonding of the diene ligand took place; namely, the original p-allyl moiety of the iron complex was changed to a more profoundly conjugated triene system including the aromatic ring and formed an h4 ligand, in order to satisfy the 18 electronic rule.