TY - JOUR
T1 - Activation of CO Using a 1,2-Disilylene
T2 - Facile Synthesis of an Abnormal N-Heterocyclic Silylene
AU - Garg, Palak
AU - Carpentier, Ambre
AU - Douair, Iskander
AU - Dange, Deepak
AU - Jiang, Yixiao
AU - Yuvaraj, K.
AU - Maron, Laurent
AU - Jones, Cameron
N1 - Funding Information:
C.J. and L.M. thank the Australian Research Council for funding. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386‐21‐1‐4048. LM is a senior member of the Institut Universtaire de France and thanks the Humboldt Foundation and the Chinese Academy of Science.
Publisher Copyright:
© 2022 Wiley-VCH GmbH
PY - 2022/5/9
Y1 - 2022/5/9
N2 - Reaction of the 1,2-disilylene, [{ArC(NDip)2}Si]2 1 (Dip=2,6-diisopropylphenyl, Ar=4-C6H4But), with CO proceeds via insertion of CO into one Si−N bond, and Si−Si bond cleavage, to cleanly give the bis(silylene), {ArC(NDip)2}Si(:)O (Formula presented.) Ar 2, under ambient conditions. The reaction can be partially reversed when solutions of 2 are subjected to UV irradiation. The five-membered heterocyclic fragment of 2 represents the first silicon analogue of an “abnormal” N-heterocyclic carbene (aNHC), a view which is substantiated by a computational analysis of the compound. Reaction of 2 with [Mo(CO)6] under UV light affords the chelate complex, [Mo(CO)4(κ2-Si,Si-2)] 3, while reaction with [Fe(CO)5] gives the unusual silyleneyl bridged complex, [{Fe2(CO)6}{μ-Si[(NDip)2CAr]}2] 4. The same coordination complexes can be accessed by reaction of 1 with [Mo(CO)6] or [Fe(CO)5] under UV light. As is the case for aNHCs, d-block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.
AB - Reaction of the 1,2-disilylene, [{ArC(NDip)2}Si]2 1 (Dip=2,6-diisopropylphenyl, Ar=4-C6H4But), with CO proceeds via insertion of CO into one Si−N bond, and Si−Si bond cleavage, to cleanly give the bis(silylene), {ArC(NDip)2}Si(:)O (Formula presented.) Ar 2, under ambient conditions. The reaction can be partially reversed when solutions of 2 are subjected to UV irradiation. The five-membered heterocyclic fragment of 2 represents the first silicon analogue of an “abnormal” N-heterocyclic carbene (aNHC), a view which is substantiated by a computational analysis of the compound. Reaction of 2 with [Mo(CO)6] under UV light affords the chelate complex, [Mo(CO)4(κ2-Si,Si-2)] 3, while reaction with [Fe(CO)5] gives the unusual silyleneyl bridged complex, [{Fe2(CO)6}{μ-Si[(NDip)2CAr]}2] 4. The same coordination complexes can be accessed by reaction of 1 with [Mo(CO)6] or [Fe(CO)5] under UV light. As is the case for aNHCs, d-block metal complexes of bis(silylene) 2 could prove useful as bespoke catalysts for organic transformations.
KW - 1,2-Disilylene
KW - Abnormal N-Heterocyclic Carbenes
KW - Bis(Silylene)
KW - Carbon Monoxide
KW - Small Molecule Activation
UR - http://www.scopus.com/inward/record.url?scp=85126230442&partnerID=8YFLogxK
U2 - 10.1002/anie.202201705
DO - 10.1002/anie.202201705
M3 - Article
AN - SCOPUS:85126230442
SN - 1433-7851
VL - 61
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 20
M1 - e202201705
ER -