Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents.

Rottschäfer D, Neumann B, Stammler H-G, Andrada DM, Ghadwal R (2020)
The Journal of organic chemistry 85(22): 14351–14359.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Phosphinidene complexes of the general formula RPM(CO)n (R = an alkyl or aryl group; M = a transition metal) are electrophilic and thermally unstable. Thus, the isolation of these elusive species for structural elucidations remains a challenge. Herein, we report the first terminal phosphinidene complexes [{(NHC)C(Ph)}P]Fe(CO)4 [NHC = IPr = C{(NDipp)CH}2 for 3; Me-IPr = C{(NDipp)CMe}2 for 4; Dipp = 2,6-iPr2C6H3; NHC = N-heterocyclic carbene] as red crystalline solids containing a pi-donor N-heterocyclic vinyl (NHV) substituent at the phosphorus atom. Calculations reveal donor-acceptor type bonding between phosphorus and iron atoms in 3 and 4. The P Fe donation represents 70% of the orbital interaction, whereas the Fe P pi-back-donation corresponds to 15% of the orbital interaction. The phosphorus atoms in 3 and 4 carry charges of +0.65e and +0.64e, respectively, indicating the electrophilic character of the phosphinidene {(NHC)C(Ph)}P moiety. Accordingly, 3 reacts with an NHC nucleophile (IMe4) to yield the Lewis adduct [{(NHC)C(Ph)}P(IMe4)]Fe(CO)4 (5) [IMe4 = C(NMeCMe)2]. The coordination of an electron-rich NHC (IMe4) to the phosphorus atom in 5 precludes the pi-electron density transfer from the NHV to the phosphorus atom. Thus, the CIPr-Cvinyl and Cvinyl-P bonds of 5 become shorter and longer, respectively, compared to those of 3.
Erscheinungsjahr
2020
Zeitschriftentitel
The Journal of organic chemistry
Band
85
Ausgabe
22
Seite(n)
14351–14359
eISSN
1520-6904
Page URI
https://pub.uni-bielefeld.de/record/2949084

Zitieren

Rottschäfer D, Neumann B, Stammler H-G, Andrada DM, Ghadwal R. Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents. The Journal of organic chemistry. 2020;85(22):14351–14359.
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D. M., & Ghadwal, R. (2020). Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents. The Journal of organic chemistry, 85(22), 14351–14359. doi:10.1021/acs.joc.0c00176
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D. M., and Ghadwal, R. (2020). Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents. The Journal of organic chemistry 85, 14351–14359.
Rottschäfer, D., et al., 2020. Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents. The Journal of organic chemistry, 85(22), p 14351–14359.
D. Rottschäfer, et al., “Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents.”, The Journal of organic chemistry, vol. 85, 2020, pp. 14351–14359.
Rottschäfer, D., Neumann, B., Stammler, H.-G., Andrada, D.M., Ghadwal, R.: Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents. The Journal of organic chemistry. 85, 14351–14359 (2020).
Rottschäfer, Dennis, Neumann, Beate, Stammler, Hans-Georg, Andrada, Diego M, and Ghadwal, Rajendra. “Isolation of Elusive Electrophilic Phosphinidene Complexes with pi-Donor N-Heterocyclic Vinyl Substituents.”. The Journal of organic chemistry 85.22 (2020): 14351–14359.

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