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Transformations of the cyclo-P4 ligand in [Cp′′′Co(η4-P4)]
Chemical Science ( IF 7.6 ) Pub Date : 2020-05-25 , DOI: 10.1039/d0sc01740j Martin Piesch 1, 2, 3, 4 , Michael Seidl 1, 2, 3, 4 , Manfred Scheer 1, 2, 3, 4
Chemical Science ( IF 7.6 ) Pub Date : 2020-05-25 , DOI: 10.1039/d0sc01740j Martin Piesch 1, 2, 3, 4 , Michael Seidl 1, 2, 3, 4 , Manfred Scheer 1, 2, 3, 4
Affiliation
The reactivity of the cyclo-P4 ligand complex [Cp′′′Co(η4-P4)] (1) (Cp′′′ = 1,2,4-tri-tert-butyl-cyclopentadienyl) towards reduction and main group nucleophiles was investigated. By using K[CpFe(CO)2], a selective reduction to the dianionic complex [(Cp′′′Co)2(μ,η3:η3-P8)]2− (2) was achieved. The reaction of 1 with tBuLi and LiCH2SiMe3 as carbon-based nucleophiles yielded [Cp′′′Co(η3-P4R)]− (R = tBu (4), CH2SiMe3 (7)), which, depending on the reaction conditions, undergo subsequent reactions with another equivalent of 1 to form [(Cp′′′Co)2(μ,η3:η3-P8R)]− (R = tBu (5), CH2SiMe3 (8)). In the case of 4, a different pathway was observed, namely a dimerisation followed by a fragmentation into [Cp′′′Co(η3-P5tBu2)]− (6) and [Cp′′′Co(η3-P3)]− (3). With OH− as an oxygen-based nucleophile, the synthesis of [Cp′′′Co(η3-P4(O)H)]− (9) was achieved. All compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy and mass spectrometry. Their electronic structures and reaction behavior were elucidated by DFT calculations.
中文翻译:
[Cp′′′Co(η4-P4)]中环P4配体的转化
所述的反应性环-P 4配体复合物的[Cp'''的Co(η 4 -P 4)](1)(CP'''= 1,2,4-三-叔丁基环戊二烯基)向还原和研究了主要的亲核试剂。通过使用K [CpFe的量(CO)2 ],选择性还原为二价阴离子配合物[(CP'''Co)的2(μ,η 3:η 3 -P 8)] 2-(2)中来实现的。的反应1与吨丁基锂和的LiCH 2森达3为基于碳的亲核试剂,得到的[Cp'''的Co(η 3-P 4 R)] --(R = t Bu(4),CH 2 SiMe 3(7)),根据反应条件,其随后与另一当量1进行反应以形成[(Cp'''Co )2(μ,η 3:η 3 -P 8 R)] -(R =吨BU(5),CH 2森达3(8))。在的情况下4,观察到不同的途径,即二聚化,随后通过碎裂成的[Cp'''的Co(η 3 -P5吨卜2)] - ( 6)和[CP'''的Co(η 3 -P 3)] - ( 3)。用OH -作为基于氧的亲核试剂,合成的[Cp'''的Co(η 3 -P 4(O)H)] - ( 9)中的溶液来实现。所有化合物均通过X射线晶体结构分析,NMR光谱和质谱进行表征。通过DFT计算阐明了它们的电子结构和反应行为。
更新日期:2020-07-08
中文翻译:
[Cp′′′Co(η4-P4)]中环P4配体的转化
所述的反应性环-P 4配体复合物的[Cp'''的Co(η 4 -P 4)](1)(CP'''= 1,2,4-三-叔丁基环戊二烯基)向还原和研究了主要的亲核试剂。通过使用K [CpFe的量(CO)2 ],选择性还原为二价阴离子配合物[(CP'''Co)的2(μ,η 3:η 3 -P 8)] 2-(2)中来实现的。的反应1与吨丁基锂和的LiCH 2森达3为基于碳的亲核试剂,得到的[Cp'''的Co(η 3-P 4 R)] --(R = t Bu(4),CH 2 SiMe 3(7)),根据反应条件,其随后与另一当量1进行反应以形成[(Cp'''Co )2(μ,η 3:η 3 -P 8 R)] -(R =吨BU(5),CH 2森达3(8))。在的情况下4,观察到不同的途径,即二聚化,随后通过碎裂成的[Cp'''的Co(η 3 -P5吨卜2)] - ( 6)和[CP'''的Co(η 3 -P 3)] - ( 3)。用OH -作为基于氧的亲核试剂,合成的[Cp'''的Co(η 3 -P 4(O)H)] - ( 9)中的溶液来实现。所有化合物均通过X射线晶体结构分析,NMR光谱和质谱进行表征。通过DFT计算阐明了它们的电子结构和反应行为。