Intra-Ligand H···F Interactions: Non-negligible Forces for Enhancing Thermostability of Cobalt Complexes in 1,3-Butadiene Polymerization
Intra-Ligand H···F Interactions: Non-negligible Forces for Enhancing Thermostability of Cobalt Complexes in 1,3-Butadiene Polymerization
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配体内 H····F 相互作用：增强 1,3-丁二烯聚合中钴配合物热稳定性的不可忽视的作用力
DOI：
10.1021/acs.organomet.2c00169
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发表时间：
2022-06
期刊：
影响因子：
2.8
通讯作者：
e Shen
中科院分区：
文献类型：
--
作者：
Liang Fang;Yanqiu Wang;Heng Liu;Xuequan Zhang;Toyoji Kakuchi;Xiaohua Wang;Xi;e Shen
解决传统的后过渡金属热稳定性差的问题对于聚烯烃和聚烯烃工业都是非常重要的。本文合成了一系列具有配体内H···F非共价相互作用的α-亚胺酮和α-二亚胺钴配合物，并对其进行了全面表征。从单晶分析中发现，这种H···F相互作用可以成功地抑制n -芳基旋转，并产生高度热鲁棒性的活性物质。在倍半氯化乙基铝存在的情况下，该配合物在100°C时也显示出较高的催化效率，优于无氟的配合物，有力地证实了配体内H···F相互作用的积极影响。此外，本研究还发现，在外部供体PPh3存在的情况下，热稳健的活性物质可以成功保留。经Lewis碱PPh3配位后，聚合物的产率也明显提高，同时，原有的1,4选择性可以转向高度的1,2选择性。
Addressing the traditional poor thermostability issues of late-transition metal is highly important for both polyolefin and polydienes industries. In this contribution, a series of α-imino-ketone and α-diimine cobalt complexes bearing intra-ligand H···F noncovalent interactions were synthesized and thoroughly characterized. From single-crystal analysis, it was found that such a H···F interaction could successfully suppress theN-aryl rotations and result in highly thermal robust active species. In the presence of ethylaluminum sesquichloride, the complexes revealed high catalytic efficiencies even at 100 °C, which is superior to fluoro-free counterparts, confirming solidly the positive influence of intra-ligand H···F interactions. Moreover, this research also disclosed that the thermal robust active species could be successfully retained in the presence of external donor PPh3. After being coordinated by the Lewis basic PPh3, the polymer yields were also appreciable, and simultaneously, the originalcis-1,4- selectivity could be shifted to a highly 1,2- manner.
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