Regioselective Insertion of Aluminum(I) in the cyclo-P 5 Ring of Pentaphosphaferrocene

A route to directly access mixed Al-Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(η -P )] (Cp*=C Me ), with two different low-valent aluminum compounds was investigated. The steric and electronic environment around the [Al ] centre are found to be crucial...

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Published in:Angewandte Chemie International Edition 2020-06, Vol.59 (24), p.9443-9447
Main Authors: Yadav, Ravi, Simler, Thomas, Goswami, Bhupendra, Schoo, Christoph, Köppe, Ralf, Dey, Subhayan, Roesky, Peter W
Format: Article
Language:English
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Summary:A route to directly access mixed Al-Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(η -P )] (Cp*=C Me ), with two different low-valent aluminum compounds was investigated. The steric and electronic environment around the [Al ] centre are found to be crucial for the formation of the resulting Al-Fe polyphosphides. Reaction with the sterically demanding [Dipp-BDIAl ] (Dipp-BDI={[2,6- Pr C H NCMe] CH} ) resulted in the first Al-based neutral triple-decker type polyphosphide complex. For [(Cp*Al ) ], an unprecedented regioselective insertion of three [Cp*Al ] moieties into two adjacent P-P bonds of the cyclo-P ring of [Cp*Fe(η -P )] was observed. The regioselectivity of the insertion reaction could be rationalized by isolating an analogue of the reaction intermediate stabilized by a strong σ-donor carbene.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202002774