Phosphasilene mediated CO activation and deoxygenative homo coupling of CO molecules in reactions with metal carbonyls

Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe 3 )(PhC(N t Bu) 2 ) ( 1 ) and its unprecedented reactivity with metal carbonyls (M = Fe, Mo, W). The reaction of 1 with Fe(CO) 5 involves the deoxygenative homocoupling of two CO molecules, for...

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Published in:Chemical science (Cambridge) 2024-11, Vol.15 (45), p.18888-18895
Main Authors: Hendi, Zohreh, Pradhan, Renuka, Rachuy, Katharina, Mahmoudi, Soheil, Pandey, Madhusudan K, Kushvaha, Saroj Kumar, Herbst-Irmer, Regine, Lourderaj, Upakarasamy, Stalke, Dietmar, Roesky, Herbert W
Format: Article
Language:English
Subjects:
Atomic properties
Atomic structure
Carbonyls
Chemical synthesis
Chemistry
Coupling (molecular)
Deoxygenation
Iron
Metal carbonyls
Molybdenum
Potential energy
Reaction mechanisms
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Summary:Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe 3 )(PhC(N t Bu) 2 ) ( 1 ) and its unprecedented reactivity with metal carbonyls (M = Fe, Mo, W). The reaction of 1 with Fe(CO) 5 involves the deoxygenative homocoupling of two CO molecules, forming a rare ketene (μ-CCO) inserted Fe complex 2 . Contrastingly, reactions with M(CO) 6 (M = Mo, W) entail the deoxygenated activation of one CO molecule, with the second CO molecule being trapped between Si and P atoms. All the compounds including their crystal structures, are thoroughly characterized and potential energy profiles for the reaction mechanisms are also explored. This paper describes the unique reactivity of phosphasilene ( 1 ) with metal carbonyls (M = Fe, Mo and W) resulting in the deoxygenative homo-coupling of two CO molecules and CO activation upon treatment with Fe ( 2 ) and W/Mo ( 3 / 4 ), respectively.
ISSN:2041-6520
2041-6539
DOI:10.1039/d4sc05491a