钼的双官能亚胺基亚烷基双吡咯化物配合物的合成及其转化为可用作开环易位聚合引发剂的双官能亚胺基亚烷基二醇盐配合物。

Synthesis of bifunctional imido alkylidene bispyrrolide complexes of molybdenum and their conversion into bifunctional imido alkylidene diolate complexes that can be employed as ROMP initiators.

作者信息

Gabert Andrea J, Schrock Richard R, Müller Peter

机构信息

Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

出版信息

Chem Asian J. 2008 Sep 1;3(8-9):1535-43. doi: 10.1002/asia.200800076.

DOI:10.1002/asia.200800076

PMID:18604823

Abstract

Addition of four equivalents of lithium 2,5-dimethylpyrrolide to a solution of Mo(NAr)(OR(F6))(2)(CHC(5)H(4))Fe (OR(F6)=OCMe(CF(3))(2)) in dichloromethane led to Mo(NAr)(Me(2)Pyr)(2)(CHC(5)H(4))Fe (2; Me(2)Pyr=2,5-dimethylpyrrolide) and lithium hexafluoro-tert-butoxide, which crystallizes out upon cooling the reaction mixture to -35 degrees C. Attempts to prepare parent pyrrolide complexes analogous to 2 resulted in the formation of a mixture of two products. The one that could be isolated contains one equivalent of lithium pyrrolide per molybdenum, that is Mo(NAr)(Pyr)(3)(CHC(5)H(4))FeLi(2) (3). The X-ray structure obtained shows it to be a dimer of dimers in which each lithium atom is bound to three pyrrolides. Addition of four equivalents of lithium 2,5-dimethylpyrrolide to Mo(NAr)(OR(F6))(2)(DME)(2)(CH-1,4-C(6)H(4)CH) (1 b) in cold DME produced Mo(NAr)(Me(2)Pyr)(2)(CH-1,4-C(6)H(4)CH) (4) in good yield, in which the bridging alkylidene is derived from 1,4-divinylbenzene. Three equivalents of (S)-H(2)[Biphen] are required for a clean reaction with 3 to form Mo(NAr)(Biphen)(CHC(5)H(4))Fe (5) (H(2)[Biphen]=3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-1,1'-biphenyl-2,2'-diol), Li(2)[Biphen], and two equivalents of pyrrole. Reactions involving 4 with the chiral diols are the best behaved. Brown Mo(NAr)(Benz(2)Bitet)(CH-1,4-C(6)H(4)CH) (6) can be isolated upon addition of (R)-H(2)[Benz(2)Bitet] (H(2)[Benz(2)Bitet]=(3,3'-dibenzhydryl-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diol) to 4, while addition of (R)-H(2)[Mes(2)Bitet] (H(2)[Mes(2)Bitet]=3,3'-dimesityl-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diol) to 4 yields Mo(NAr)(Mes(2)Bitet)(CH-1,4-C(6)H(4)CH) (7). Compounds 5, 6, and 7 were employed as initiators for the polymerization of 2,3-dicarbomethoxynorbornadiene (DCMNBD) and 2,3-bis(trifluoromethyl)norbornadiene (NBDF6).

摘要

向二氯甲烷中Mo(NAr)(OR(F6))(2)(CHC(5)H(4))Fe（OR(F6)=OCMe(CF(3))(2)）的溶液中加入四当量的2,5 - 二甲基吡咯锂，得到Mo(NAr)(Me(2)Pyr)(2)(CHC(5)H(4))Fe（2；Me(2)Pyr = 2,5 - 二甲基吡咯锂）和六氟叔丁醇锂，将反应混合物冷却至 - 35℃时，六氟叔丁醇锂结晶析出。尝试制备与2类似的母体吡咯配合物导致形成两种产物的混合物。可分离得到的一种产物是每摩尔钼含有一当量吡咯锂，即Mo(NAr)(Pyr)(3)(CHC(5)H(4))FeLi(2)（3）。所获得的X射线结构表明它是二聚体的二聚体，其中每个锂原子与三个吡咯配位。在冷的1,2 - 二甲氧基乙烷中，向Mo(NAr)(OR(F6))(2)(DME)(2)(CH - 1,4 - C(6)H(4)CH)（1b）中加入四当量的2,5 - 二甲基吡咯锂，以良好的产率得到Mo(NAr)(Me(2)Pyr)(2)(CH - 1,4 - C(6)H(4)CH)（4），其中桥连亚烷基源自1,4 - 二乙烯基苯。与3进行完全反应需要三当量的(S)-H(2)[Biphen]以形成Mo(NAr)(Biphen)(CHC(5)H(4))Fe（5）（H(2)[Biphen]=3,3'-二叔丁基 - 5,5',6,6'-四甲基 - 1,1'-联苯 - 2,2'-二醇）、Li(2)[Biphen]和两当量的吡咯。涉及4与手性二醇的反应表现最佳。加入(R)-H(2)[Benz(2)Bitet]（H(2)[Benz(2)Bitet]=(3,3'-二苯甲基 - 5,5',6,6',7,7',8,8'-八氢 - 1,1'-联萘 - 2,2'-二醇）到4中可分离得到Brown Mo(NAr)(Benz(2)Bitet)(CH - 1,4 - C(6)H(4)CH)（6），而向4中加入(R)-H(2)[Mes(2)Bitet]（H(2)[Mes(2)Bitet]=3,3'-二叔丁基 - 5,5',6,6',7,7',8,8'-八氢 - 1,1'-联萘 - 2,2'-二醇）得到Mo(NAr)(Mes(2)Bitet)(CH - 1,4 - C(6)H(4)CH)（7）。化合物5、6和7被用作2,3 - 二羧基甲氧基降冰片二烯（DCMNBD）和2,3 - 双（三氟甲基）降冰片二烯（NBDF6）聚合反应的引发剂。