Synthesis of a Nickel(I) alkoxide and related cation equivalents
Synthesis of a Nickel(I) alkoxide and related cation equivalents
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DOI：
10.1016/j.poly.2021.115408
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发表时间：
2021-11
期刊：
影响因子：
2.6
通讯作者：
Neil A. Dodd;J. Bacsa;J. Sadighi
中科院分区：
文献类型：
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作者：
Neil A. Dodd;J. Bacsa;J. Sadighi
六甲基二硅氮基镍（I）（N-杂环卡宾）使新戊醇（NpOH）去质子化以形成相应的新戊氧基镍（I），其结晶为烷氧基桥接的二聚体。二聚体与1当量的三氟甲磺酸叔丁基二甲基硅烷基酯反应，生成以CF_3SO_3（OTf）阴离子为桥连的烷氧基桥联的二镍（I）配合物。在[LNiONp] 2和[（LNi）2（μ-ONp）（μ-OTf）]中，Ni···Ni距离与金属-金属键的缺失一致，Evans NMR数据与S = 1自旋态一致.相反，用两当量的三氟甲硅烷基酯处理二聚体会导致完全提取醇盐。加入乙醚形成单体d9络合物LNi（OEt 2）OTf。
An (N-heterocyclic carbene)nickel(I) hexamethyldisilazide deprotonates neopentanol (NpOH) to form the corresponding nickel(I) neopentoxide, which crystallizes as an alkoxide-bridged dimer. Reaction of the dimer with one equivalent oftert-butyldimethylsilyl trifluoromethanesulfonate gives an alkoxide-bridged dinickel(I) complex bridged by the CF3SO3(OTf) anion. In both [LNiONp]2and [(LNi)2(μ-ONp)(μ-OTf)], Ni•••Ni distances are consistent with the absence of metal–metal bonding, and Evans NMR data are consistent with theS= 1 spin state. Treatment of the dimer with two equivalents of silyl triflate results instead in complete abstraction of alkoxide. Addition of diethyl ether forms the monomeric d9complex LNi(OEt2)OTf.