Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex

Ghadwal R, Rottschäfer D, Andrada DM, Frenking G, Schuermann CJ, Stammler H-G (2017)
DALTON TRANSACTIONS 46(24): 7791-7799.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The synthesis and characterization of the N-heterocyclic carbene (NHC) stabilized dichlorosilylene Group 6 metal complexes {(IPr) SiCl2} W(CO)(5) (3-W), {(IPr) SiCl2} 2Cr(CO) 4 (4-Cr), and {(IPr) SiCl2} 2W(CO) 4 (4-W) (IPr = 1,3-bis(2,6-diisopropylphenyl) imidazol-2-ylidene) are reported. Treatment of 3-W with CsOH in the presence of IPr leads to the formation of an abnormal-NHC (aNHC) metal complex (aIPr(H)) W(CO) 5 (6-W) (aIPr(H) = 1,3-bis(2,6-diisopropylphenyl) imidazol-4-ylidene), unveiling an unprecedented normal-toabnormal transformation route of an NHC. DFT calculations support the proposed mechanism that involves CsOH mediated deprotonation of the IPr-backbone of 3-W to yield a ditopic carbanionic-NHC (dcNHC) complex 5a-W. Subsequent 1,4-migration of the W(CO)(5) moiety and hydrolysis of the unmasked SiCl2 rationalize the formation of 6-W. The desired H2O molecule is generated in the initial step on deprotonation of IPr with CsOH. In contrast to the literature precedents, the calculations indicate that the abnormal complex 6-W is 13.5 kcal mol(-1) thermodynamically higher in energy than the normal counterpart (IPr) W(CO)(5) (8-W). Interestingly, as the aNHC-compounds reported so far are more stable than their normal counterparts, this finding showcases an opposite trend. Moreover, reaction pathways to the synthesized and related complexes have been investigated by DFT calculations.
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Zeitschriftentitel
DALTON TRANSACTIONS
Band
46
Zeitschriftennummer
24
Seite
7791-7799
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Ghadwal R, Rottschäfer D, Andrada DM, Frenking G, Schuermann CJ, Stammler H-G. Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex. DALTON TRANSACTIONS. 2017;46(24):7791-7799.
Ghadwal, R., Rottschäfer, D., Andrada, D. M., Frenking, G., Schuermann, C. J., & Stammler, H. - G. (2017). Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex. DALTON TRANSACTIONS, 46(24), 7791-7799. doi:10.1039/c7dt01199g
Ghadwal, R., Rottschäfer, D., Andrada, D. M., Frenking, G., Schuermann, C. J., and Stammler, H. - G. (2017). Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex. DALTON TRANSACTIONS 46, 7791-7799.
Ghadwal, R., et al., 2017. Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex. DALTON TRANSACTIONS, 46(24), p 7791-7799.
R. Ghadwal, et al., “Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex”, DALTON TRANSACTIONS, vol. 46, 2017, pp. 7791-7799.
Ghadwal, R., Rottschäfer, D., Andrada, D.M., Frenking, G., Schuermann, C.J., Stammler, H.-G.: Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex. DALTON TRANSACTIONS. 46, 7791-7799 (2017).
Ghadwal, Rajendra, Rottschäfer, Dennis, Andrada, Diego M., Frenking, Gernot, Schuermann, Christian J., and Stammler, Hans-Georg. “Normal-to-abnormal rearrangement of an N-heterocyclic carbene with a silylene transition metal complex”. DALTON TRANSACTIONS 46.24 (2017): 7791-7799.

4 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Silylene-Functionalized N-Heterocyclic Carbene (Si-NHC).
Rottschäfer D, Blomeyer S, Neumann B, Stammler HG, Ghadwal RS., Chemistry 24(2), 2018
PMID: 28833705
The Viability of C5-Protonated- and C4,C5-Ditopic Carbanionic Abnormal NHCs: A New Dimension in NHC Chemistry.
Rottschäfer D, Ebeler F, Strothmann T, Neumann B, Stammler HG, Mix A, Ghadwal RS., Chemistry 24(15), 2018
PMID: 29363830
N-Heterocyclic Vinylidene-Stabilized Phosphorus Biradicaloid.
Rottschäfer D, Neumann B, Stammler HG, Ghadwal RS., Chemistry 23(38), 2017
PMID: 28556982
Nickel-catalysed direct C2-arylation of N-heterocyclic carbenes.
Ho NKT, Neumann B, Stammler HG, Menezes da Silva VH, Watanabe DG, Braga AAC, Ghadwal RS., Dalton Trans 46(36), 2017
PMID: 28853488

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