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Tris(butadiene) Metal Complexes of the First-Row Transition Metals versus Coupling of Butadiene to Eight- and Twelve-Carbon Hydrocarbon Chains
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2019-06-10 00:00:00 , DOI: 10.1021/acs.jpca.9b03063 Qunchao Fan 1 , Huidong Li 1 , Jia Fu 1 , Zhixiang Fan 1 , Yonggen Xu 1 , Hao Feng 1 , Yaoming Xie 2 , R. Bruce King 2 , Henry F. Schaefer 2
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2019-06-10 00:00:00 , DOI: 10.1021/acs.jpca.9b03063 Qunchao Fan 1 , Huidong Li 1 , Jia Fu 1 , Zhixiang Fan 1 , Yonggen Xu 1 , Hao Feng 1 , Yaoming Xie 2 , R. Bruce King 2 , Henry F. Schaefer 2
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The role that zerovalent nickel plays in catalyzing the trimerization of butadiene to 1,5,9-cyclododecatriene conveys interest in the properties of the tris(butadiene)metal complexes (C4H6)3M. In this connection the complexes (C4H6)3M (M = Ti–Ni) of the first-row transition metals have been investigated by density functional theory. The intermediate C12H18Ni which has been isolated in the nickel-catalyzed trimerization of butadiene but is too unstable for X-ray crystallography is suggested here to have an open-chain hexahapto η3,3-C12H18 ligand rather than the octahapto such ligand suggested by some investigators. The lowest energy (C4H6)3M structures of the other first-row transition metals from vanadium to cobalt are found to have related structures with open-chain C12H18 ligands having hapticities ranging from four to eight with hexahapto structures being most common. The nickel and cobalt (C12H18)M derivatives favor low-spin singlet and doublet spin states, respectively, whereas the manganese derivative (C12H18)Mn favors the high-spin sextet state corresponding to the half-filled d5 shell of Mn(II). A (C4H6)3Cr structure with three separate tetrahapto butadiene ligands analogous to the very stable (η4-C4H6)3M (M = Mo, W) with the favored 18-electron metal configuration is found to be a very high energy structure relative to isomers containing an open-chain C12H18 ligand.
中文翻译：
第一行过渡金属的三（丁二烯）金属配合物与丁二烯与八碳和十二碳烃链的偶联
零价镍在催化丁二烯向1,5,9-环十二碳三烯的三聚反应中的作用引起了人们对三（丁二烯）金属配合物（C 4 H 6）3 M的性质的兴趣。在这种情况下，配合物（C 4 H 6）3 M（M = Ti-Ni）第一行过渡金属已经通过密度泛函理论进行了研究。中间体C 12 ħ 18的Ni已经分离在丁二烯的镍催化的三聚，但太不稳定用于X射线晶体学，这里建议为具有开链hexahaptoη 3,3 -C 12 ħ 18配体而不是某些研究者建议的八配体这样的配体。发现从钒到钴的其他第一行过渡金属的最低能级（C 4 H 6）3 M结构具有相关的结构，其开链C 12 H 18配体的触觉范围为4至8，六触键结构为最常见的。镍和钴（C 12 H 18）M衍生物分别有利于低自旋单重态和双峰自旋态，而锰衍生物（C 12 H 18）Mn则倾向于对应于半填充d 5的高自旋六重态。Mn（II）的壳。A（C4 ħ 6）3的Cr结构与三个单独的tetrahapto丁二烯配体类似于非常稳定的（η 4 -C 4 H ^ 6）3 M（M =钼，钨）与偏爱18电子金属结构被发现是一个非常相对于含有开链C 12 H 18配体的异构体而言，具有高能量结构。
更新日期：2019-06-10
中文翻译：
第一行过渡金属的三（丁二烯）金属配合物与丁二烯与八碳和十二碳烃链的偶联
零价镍在催化丁二烯向1,5,9-环十二碳三烯的三聚反应中的作用引起了人们对三（丁二烯）金属配合物（C 4 H 6）3 M的性质的兴趣。在这种情况下，配合物（C 4 H 6）3 M（M = Ti-Ni）第一行过渡金属已经通过密度泛函理论进行了研究。中间体C 12 ħ 18的Ni已经分离在丁二烯的镍催化的三聚，但太不稳定用于X射线晶体学，这里建议为具有开链hexahaptoη 3,3 -C 12 ħ 18配体而不是某些研究者建议的八配体这样的配体。发现从钒到钴的其他第一行过渡金属的最低能级（C 4 H 6）3 M结构具有相关的结构，其开链C 12 H 18配体的触觉范围为4至8，六触键结构为最常见的。镍和钴（C 12 H 18）M衍生物分别有利于低自旋单重态和双峰自旋态，而锰衍生物（C 12 H 18）Mn则倾向于对应于半填充d 5的高自旋六重态。Mn（II）的壳。A（C4 ħ 6）3的Cr结构与三个单独的tetrahapto丁二烯配体类似于非常稳定的（η 4 -C 4 H ^ 6）3 M（M =钼，钨）与偏爱18电子金属结构被发现是一个非常相对于含有开链C 12 H 18配体的异构体而言，具有高能量结构。
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