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

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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,η33-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,η33-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.

Graphical abstract: Transformations of the cyclo-P4 ligand in [Cp′′′Co(η4-P4)]

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Article information


Submitted
25 Mar 2020
Accepted
23 May 2020
First published
25 May 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

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

M. Piesch, M. Seidl and M. Scheer, Chem. Sci., 2020, Advance Article , DOI: 10.1039/D0SC01740J

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