Journal article
Regioselective Insertion of Aluminum(I) in the cyclo-P-5 Ring of Pentaphosphaferrocene
Publication Details
Authors: | Dey, S. |
Publisher: | WILEY-V C H VERLAG GMBH |
Publication year: | 2020 |
Journal: | Angewandte Chemie |
Pages range : | 9443-9447 |
Volume number: | 59 |
Issue number: | 24 |
Start page: | 9443 |
End page: | 9447 |
Number of pages: | 5 |
ISSN: | 1433-7851 |
DOI-Link der Erstveröffentlichung: |
Abstract
A route to directly access mixed Al-Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(eta(5)-P-5)] (Cp*=C5Me5), with two different low-valent aluminum compounds was investigated. The steric and electronic environment around the [Al-I] centre are found to be crucial for the formation of the resulting Al-Fe polyphosphides. Reaction with the sterically demanding [Dipp-BDIAlI] (Dipp-BDI={[2,6-(Pr2C6H3NCMe)-Pr-i](2)CH}(-)) resulted in the first Al-based neutral triple-decker type polyphosphide complex. For [(Cp*Al-I)(4)], an unprecedented regioselective insertion of three [Cp*Al-III](2+) moieties into two adjacent P-P bonds of the cyclo-P-5 ring of [Cp*Fe(eta(5)-P-5)] was observed. The regioselectivity of the insertion reaction could be rationalized by isolating an analogue of the reaction intermediate stabilized by a strong sigma-donor carbene.
A route to directly access mixed Al-Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(eta(5)-P-5)] (Cp*=C5Me5), with two different low-valent aluminum compounds was investigated. The steric and electronic environment around the [Al-I] centre are found to be crucial for the formation of the resulting Al-Fe polyphosphides. Reaction with the sterically demanding [Dipp-BDIAlI] (Dipp-BDI={[2,6-(Pr2C6H3NCMe)-Pr-i](2)CH}(-)) resulted in the first Al-based neutral triple-decker type polyphosphide complex. For [(Cp*Al-I)(4)], an unprecedented regioselective insertion of three [Cp*Al-III](2+) moieties into two adjacent P-P bonds of the cyclo-P-5 ring of [Cp*Fe(eta(5)-P-5)] was observed. The regioselectivity of the insertion reaction could be rationalized by isolating an analogue of the reaction intermediate stabilized by a strong sigma-donor carbene.
Keywords
ferrocene, polyphosphides, regioselectivity, triple-decker
