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

Zohreh Hendi; Renuka Pradhan; Katharina Rachuy; Soheil Mahmoudi; Madhusudan K Pandey; Saroj Kumar Kushvaha; Regine Herbst-Irmer; Upakarasamy Lourderaj; Dietmar Stalke; Herbert W Roesky

doi:10.1039/d4sc05491a

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

Zohreh Hendi, Renuka Pradhan, Katharina Rachuy, Soheil Mahmoudi, Madhusudan K Pandey, Saroj Kumar Kushvaha, Regine Herbst-Irmer, Upakarasamy Lourderaj (Corresponding author), Dietmar Stalke (Corresponding author), Herbert W Roesky (Corresponding author)

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Abstract

Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe3)(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.

Original language	English
Pages (from-to)	18888-18895
Number of pages	8
Journal	Chemical Science
Volume	15
Issue number	45
Early online date	10 Oct 2024
DOIs	https://doi.org/10.1039/d4sc05491a
Publication status	Published - 10 Oct 2024

Austrian Fields of Science 2012

104003 Inorganic chemistry
204001 Inorganic chemical technology

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10.1039/d4sc05491a

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title = "Phosphasilene mediated CO activation and deoxygenative homo coupling of CO molecules in reactions with metal carbonyls",

abstract = "Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe3)(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.",

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TY - JOUR

T1 - Phosphasilene mediated CO activation and deoxygenative homo coupling of CO molecules in reactions with metal carbonyls

AU - Hendi, Zohreh

AU - Pradhan, Renuka

AU - Rachuy, Katharina

AU - Mahmoudi, Soheil

AU - Pandey, Madhusudan K

AU - Kushvaha, Saroj Kumar

AU - Herbst-Irmer, Regine

AU - Lourderaj, Upakarasamy

AU - Stalke, Dietmar

AU - Roesky, Herbert W

PY - 2024/10/10

Y1 - 2024/10/10

N2 - Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe3)(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.

AB - Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe3)(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.

UR - http://www.scopus.com/inward/record.url?scp=85207340074&partnerID=8YFLogxK

U2 - 10.1039/d4sc05491a

DO - 10.1039/d4sc05491a

M3 - Article

C2 - 39430926

SN - 2041-6520

VL - 15

SP - 18888

EP - 18895

JO - Chemical Science

JF - Chemical Science

IS - 45

ER -

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

Abstract

Austrian Fields of Science 2012

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