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The Reactivity of Mercapto Groups against Boron Hydrides in Pincer Ligated Nickel Mercapto Complexes
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-09-14 , DOI: 10.1002/asia.201801050 Jie Zhang 1 , Ting Liu 1 , Changgeng Wei 1 , Jiarui Chang 1 , Qiang-Qiang Ma 1 , Shujun Li 1 , Nana Ma 1 , Xuenian Chen 1
Chemistry - An Asian Journal ( IF 3.5 ) Pub Date : 2018-09-14 , DOI: 10.1002/asia.201801050 Jie Zhang 1 , Ting Liu 1 , Changgeng Wei 1 , Jiarui Chang 1 , Qiang-Qiang Ma 1 , Shujun Li 1 , Nana Ma 1 , Xuenian Chen 1
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Several pincer ligated nickel mercapto complexes, [2,6‐(R2PCH2)2C6H3]NiSH (R=tBu, 1 a; iPr, 1 b), [2,6‐(R2PO)2C6H3]NiSH (R=tBu, 2 a; iPr, 2 b) and [4‐MeOCO‐2,6‐(tBu2PO)2C6H2]NiSH (3 a), were synthesized and fully characterized. The reactivity of the mercapto groups against boron hydrides and organic bases was investigated. It was found that the mercapto groups are difficult to be deprotonated by boron hydrides or organic bases. The treatment of complex 2 a or 2 b with an excess amount of catecholborane (HBcat) afforded the corresponding pincer ligated nickel borohydride complexes and the HBcat degradation product. The treatment of complex 1 a, 2 a or 2 b with an excess amount of BH3⋅THF produced the corresponding nickel borohydride species and the S‐bridged triborane species THF⋅BH2‐μ2‐S(B2H5) (5). No reactions between these complexes and organic bases were observed. DFT calculations were carried out to understand this reactivity and get mechanistic insights into the reactions.
中文翻译：
巯基连接的巯基镍配合物中巯基对硼氢化物的反应性。
几种钳形连接的巯基镍配合物[2,6-（R 2 PCH 2）2 C 6 H 3 ] NiSH（R = t Bu，1 a ; i Pr，1 b），[2,6-（R 2 PO ）2 C 6 H 3 ] NiSH（R = t Bu，2 a ; i Pr，2 b）和[4-MeOCO-2,6-（t Bu 2 PO）2 C 6 H 2 ] NiSH（3 a），进行了合成并进行了充分表征。研究了巯基对氢化硼和有机碱的反应性。发现巯基很难被氢化硼或有机碱去质子化。复合物的治疗 2或2b中与过量的量的儿茶酚硼烷（HBcat），得到相应的钳结扎硼氢化镍络合物和HBcat降解产物。的复杂的处理 1，2或图2b与BH过量3 ⋅THF产生相应的硼氢化镍物种和S-桥接triborane物种THF⋅BH 2 - μ 2 -S（B2 H 5）（5）。在这些配合物和有机碱之间未观察到反应。进行DFT计算是为了了解这种反应性并获得对反应的机械见解。
更新日期：2018-09-14
中文翻译：
巯基连接的巯基镍配合物中巯基对硼氢化物的反应性。
几种钳形连接的巯基镍配合物[2,6-（R 2 PCH 2）2 C 6 H 3 ] NiSH（R = t Bu，1 a ; i Pr，1 b），[2,6-（R 2 PO ）2 C 6 H 3 ] NiSH（R = t Bu，2 a ; i Pr，2 b）和[4-MeOCO-2,6-（t Bu 2 PO）2 C 6 H 2 ] NiSH（3 a），进行了合成并进行了充分表征。研究了巯基对氢化硼和有机碱的反应性。发现巯基很难被氢化硼或有机碱去质子化。复合物的治疗 2或2b中与过量的量的儿茶酚硼烷（HBcat），得到相应的钳结扎硼氢化镍络合物和HBcat降解产物。的复杂的处理 1，2或图2b与BH过量3 ⋅THF产生相应的硼氢化镍物种和S-桥接triborane物种THF⋅BH 2 - μ 2 -S（B2 H 5）（5）。在这些配合物和有机碱之间未观察到反应。进行DFT计算是为了了解这种反应性并获得对反应的机械见解。
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