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Nonsymmetrical Benzene–Pyridine-Based Nickel Pincer Complexes Featuring Borohydride, Formate, Ethyl, and Nitrosyl Ligands
Organometallics ( IF 2.5 ) Pub Date : 2021-09-17 , DOI: 10.1021/acs.organomet.1c00441 Daniel Himmelbauer 1 , Heiko Schratzberger 1 , Matthias G. Käfer 1 , Berthold Stöger 2 , Luis F. Veiros 3 , Karl Kirchner 1
Organometallics ( IF 2.5 ) Pub Date : 2021-09-17 , DOI: 10.1021/acs.organomet.1c00441 Daniel Himmelbauer 1 , Heiko Schratzberger 1 , Matthias G. Käfer 1 , Berthold Stöger 2 , Luis F. Veiros 3 , Karl Kirchner 1
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Nonsymmetrical nickel PCN pincer complexes [Ni(iPrPCNX)Cl] (X = NMe, CH2) are obtained by metalation of the benzene–pyridine-based pincer ligand iPrPCNX (X = NMe, CH2) with [Ni(dme)Cl2] (dme = 1,2-dimethoxyethane). These nickel species afforded the respective borohydride and ethyl complexes [Ni(iPrPCNX)L] (L = BH4, Et) upon treatment with NaBH4 and EtMgBr (or Et2Mg), respectively. Reacting [Ni(iPrPCNX)(κ2-BH4)] with CO2 gave the formate complexes [Ni(iPrPCNX)(OCHO)]. Treatment of [Ni(iPrPCNX)Cl] with the nitrosyl salt NOBF4 led to the formation of the unusual cationic square-pyramidal nickel nitrosyl pincer complexes [Ni(iPrPCNX)(NO)Cl]+ featuring a strongly bent NO ligand (∠Ni–N–O 128.5°). These systems can be described as {NiNO}10 according to the Enemark–Feltham convention. Despite of the bent nature of the NO ligand the νNO is observed at 1849 cm–1 which is more typical for a linear Ni–N–O arrangement. The structure of these complexes is rationalized by means of DFT calculations. The molecular structures of representative complexes are presented.
中文翻译：
具有硼氢化物、甲酸盐、乙基和亚硝基配体的非对称苯-吡啶基镍钳配合物
非对称镍 PCN 钳形配合物 [Ni( i Pr PCN X )Cl] (X = NMe, CH 2 ) 通过苯-吡啶类钳形配体i Pr PCN X (X = NMe, CH 2 ) 与 [ Ni(dme)Cl 2 ] (dme = 1,2-二甲氧基乙烷)。这些镍物种分别在用 NaBH 4和 EtMgBr（或 Et 2 Mg）处理后提供相应的硼氢化物和乙基配合物 [Ni( i Pr PCN X )L] (L = BH 4 , Et) 。反应 [Ni( i Pr PCN X )(κ 2-BH 4 )]与CO 2得到甲酸盐配合物[Ni( i Pr PCN X )(OCHO)]。的治疗[镍（我镨PCN X）CL]与亚硝酰盐NOBF 4导致形成的不寻常的阳离子四方锥镍的亚硝酰基钳形络合物[镍（我镨PCN X）（NO）CL] +设有强弯曲 NO 配体 (∠Ni–N–O 128.5°)。根据 Enemark-Feltham 约定，这些系统可以描述为 {NiNO} 10。尽管 NO 配体具有弯曲性质，但在 1849 cm –1处观察到了 ν NO这对于线性 Ni-N-O 排列更为典型。这些复合体的结构通过 DFT 计算进行了合理化。介绍了代表性配合物的分子结构。
更新日期：2021-10-11
中文翻译：
具有硼氢化物、甲酸盐、乙基和亚硝基配体的非对称苯-吡啶基镍钳配合物
非对称镍 PCN 钳形配合物 [Ni( i Pr PCN X )Cl] (X = NMe, CH 2 ) 通过苯-吡啶类钳形配体i Pr PCN X (X = NMe, CH 2 ) 与 [ Ni(dme)Cl 2 ] (dme = 1,2-二甲氧基乙烷)。这些镍物种分别在用 NaBH 4和 EtMgBr（或 Et 2 Mg）处理后提供相应的硼氢化物和乙基配合物 [Ni( i Pr PCN X )L] (L = BH 4 , Et) 。反应 [Ni( i Pr PCN X )(κ 2-BH 4 )]与CO 2得到甲酸盐配合物[Ni( i Pr PCN X )(OCHO)]。的治疗[镍（我镨PCN X）CL]与亚硝酰盐NOBF 4导致形成的不寻常的阳离子四方锥镍的亚硝酰基钳形络合物[镍（我镨PCN X）（NO）CL] +设有强弯曲 NO 配体 (∠Ni–N–O 128.5°)。根据 Enemark-Feltham 约定，这些系统可以描述为 {NiNO} 10。尽管 NO 配体具有弯曲性质，但在 1849 cm –1处观察到了 ν NO这对于线性 Ni-N-O 排列更为典型。这些复合体的结构通过 DFT 计算进行了合理化。介绍了代表性配合物的分子结构。
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