SYNTHESIS OF ALLYLNICKEL ARYLOXIDES AND ARENETHIOLATES - STUDY OF THEIR DYNAMIC ISOMERIZATION AND 1,3-DIENE POLYMERIZATION ACTIVITY
SYNTHESIS OF ALLYLNICKEL ARYLOXIDES AND ARENETHIOLATES - STUDY OF THEIR DYNAMIC ISOMERIZATION AND 1,3-DIENE POLYMERIZATION ACTIVITY
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DOI：
10.1021/om00017a073
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发表时间：
1994-05-01
期刊：
影响因子：
2.8
通讯作者：
CLAVERIE, JP
中科院分区：
文献类型：
--
作者：
HAMPTON, PD;WU, S;CLAVERIE, JP
烯丙基镍 (II) 络合物的新家族，[Ni(eta3-烯丙基)(mu-X)]2 (X = ArO, ArS)，通过芳氧化物或芳烃硫醇的钠盐或锂盐与 [Ni(eta3-烯丙基)(mu-Br)]2 的阴离子复分解合成。该复合物被认为是二聚体并且由顺式和反式异构体的混合物组成。动态过程可在 H-1 NMR 时间尺度上快速平衡五氟苯酚盐、2,6-二氟苯酚盐和 3,5-双（三氟甲基）苯酚盐络合物的顺式和反式异构体。 2,6-二甲基苯氧基、2,6-二异丙苯氧基、2,4,6-三(三氟甲基)苯氧基和五氟噻吩氧基络合物在室温下是静态的。 3,5-双(三氟甲基)苯酚盐络合物的变温核磁共振研究提供的活化焓和熵值分别为12.9 kcal/mol和-6.6 cal/(K mol)。提议将其中一个 mu-X 桥的烯丙基旋转或裂解作为异构化的机制。五氟苯酚盐、3,5-双(三氟甲基)苯酚盐和2,4,6-三(三氟甲基)苯酚盐络合物引发1,3-环己二烯和1,3-丁二烯的快速聚合，形成高分子量1,4-连接聚合物。
A new family of allylnickel(II) complexes, [Ni(eta3-allyl)(mu-X)]2 (X = ArO, ArS), have been synthesized by anion metathesis of the sodium or lithium salts of aryloxides or arenethiolates with[Ni(eta3-allyl)(mu-Br)]2. The complexes are proposed to be dimeric and to consist of a mixture of cis and trans isomers. A dynamic process rapidly equilibrates the cis and trans isomers of the pentafluorophenoxide, 2,6-difluorophenoxide, and 3,5-bis(trifluoromethyl)phenoxide complexes on the H-1 NMR time scale. The 2,6-dimethylphenoxide, 2,6-diisopropylphenoxide, 2,4,6-tris(trifluoromethyl)phenoxide, and pentafluorothiophenoxide complexes are static at room temperature. A variable-temperature NMR study of the 3,5-bis(trifluoromethyl)phenoxide complex provided activation enthalpy and entropy values of 12.9 kcal/mol and -6.6 cal/(K mol), respectively. Allyl rotation or cleavage of one of the mu-X bridges is proposed as the mechanism for the isomerization. The pentafluorophenoxide, 3,5-bis(trifluoromethyl)phenoxide, and 2,4,6-tris(trifluoromethyl)phenoxide complexes initiate the rapid polymerization of 1,3-cyclohexadiene and 1,3-butadiene to form high-molecular weight, 1,4-linked polymers.