Heteroleptic nickel complexes of a bulky bis(carbene)borate ligand
Heteroleptic nickel complexes of a bulky bis(carbene)borate ligand
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DOI：
10.1016/j.poly.2018.09.026
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发表时间：
2018-12
期刊：
影响因子：
2.6
通讯作者：
Jorge L. Martinez;W. Lee;M. Pink;Chun-Hsing Chen;Jeremy M. Smith
中科院分区：
文献类型：
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作者：
Jorge L. Martinez;W. Lee;M. Pink;Chun-Hsing Chen;Jeremy M. Smith
通过双卡宾硼酸盐配体转移到镍亚硝酰基合成子Ni（NO）（PPh 3）2Br上，得到了新的镍亚硝酰基配合物Ph 2B（tBuIm）2Ni（NO）（PPh 3）。的固态结构揭示了一个三角锥镍离子与一个非常长的键的顶端PPh 3配体。该配合物在溶液中可逆地解离PPh 3，得到三配位的Ph 2B（tBuIm）2Ni（NO），NMR数据为低温下PPh 3的结合提供了证据.配体转移到Ni（PMe 3）2Cl 2提供正方形平面配合物Ph 2B（tBuIm）2Ni（PMe 3）Cl，其没有显示重排以形成具有两个双（卡宾）硼酸盐配体的均配配合物的证据。该配合物是[Ph 2B（tBuIm）2Ni]+片段的合适合成子，如π-烯丙基配合物Ph 2B（tBuIm）2Ni（η3-C7 H7）的合成所证明的。π-烯丙基络合物与O2反应生成苯甲醛和一种不稳定的络合物，初步确定为氢氧化镍[Ph 2B（tBuIm）2Ni（μ-OH）]2。
Bis(carbene)borate ligand transfer to the nickel nitrosyl synthon Ni(NO)(PPh3)2Br provides the new nickel nitrosyl complex Ph2B(tBuIm)2Ni(NO)(PPh3). The solid state structure reveals a trigonal pyramidal nickel ion with a very long bond to the apical PPh3ligand. The complex reversibly dissociates PPh3in solution to afford three-coordinate Ph2B(tBuIm)2Ni(NO), with NMR data providing evidence for PPh3binding at low temperatures. Ligand transfer to Ni(PMe3)2Cl2provides the square planar complex, Ph2B(tBuIm)2Ni(PMe3)Cl, which shows no evidence for rearranging to the form a homoleptic complex with two bis(carbene)borate ligands. This complex is a suitable synthon for the [Ph2B(tBuIm)2Ni]+fragment, as demonstrated by the synthesis of the π-allyl complex Ph2B(tBuIm)2Ni(η3-C7H7). The π-allyl complex reacts with O2to provide benzaldehyde and an unstable complex that is tentatively identified as the nickel(II) hydroxide [Ph2B(tBuIm)2Ni(μ-OH)]2.