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-P₅^tBu₂)]⁻ (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：

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[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。