Transformations of the cyclo-P4 ligand in [Cp'''Co(η4-P4)].

Chemical Science
Martin PieschManfred Scheer

Abstract

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 t BuLi and LiCH2SiMe3 as carbon-based nucleophiles yielded [Cp'''Co(η3-P4R)]- (R = t Bu (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 = t Bu (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 t Bu2)]- (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.

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Oct 2, 2019·Angewandte Chemie·Martin PieschManfred Scheer
Oct 2, 2019·Angewandte Chemie·Christian M HoidnRobert Wolf

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Citations

Nov 3, 2020·Chemistry : a European Journal·Christian M HoidnRobert Wolf
Mar 19, 2021·Inorganic Chemistry·Anna GarbagnatiManfred Scheer

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Methods Mentioned

BETA
NMR
X-ray

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