Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides

Rottschäfer D, Blomeyer S, Neumann B, Stammler H-G, Ghadwal R (2019)
CHEMICAL SCIENCE 10(48): 11078-11085.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Abstract / Bemerkung
A series of unique C2P3-ring compounds [(ADC(Ar))P-3] (ADC(Ar) = ArC{(DippN)C}(2); Dipp = 2,6-iPr(2)C(6)H(3); Ar = Ph 4a, 3-MeC(6)H(4)4b, 4-MeC(6)H(4)4c, and 4-Me(2)NC(6)H(4)4d) are readily accessible in an almost quantitative yield by the direct functionalization of white phosphorus (P-4) with appropriate anionic dicarbenes [Li(ADC(Ar))]. The formation of 1,2,3-triphosphol-2-ides (4a-4d) suggests unprecedented [3 + 1] fragmentation of P-4 into P-3(+) and P-. The P-3(+) cation is trapped by the (ADC(Ar))(-) to give 4, while the putative P- anion reacts with additional P-4 to yield the Li3P7 species, a useful reagent in the synthesis of organophosphorus compounds. Remarkably, the P-4 fragmentation is also viable with the related mesoionic carbenes (iMICs(Ar)) (iMIC(Ar) = ArC{(DippN)(2)CCH}, i stands for imidazole-based) giving rise to 4. DFT calculations reveal that both the C3N2 and C2P3-rings of 4 are 6 pi-electron aromatic systems. The natural bonding orbital (NBO) analyses indicate that compounds 4 are mesoionic species featuring a negatively polarized C2P3-ring. The HOMO-3 of 4 is mainly the lone-pair at the central phosphorus atom that undergoes sigma-bond formation with a variety of metal-electrophiles to yield complexes [{(ADC(Ar))P-3}M(CO)(n)] (M = Fe, n = 4, Ar = Ph 5a or 4-Me-C(6)H(4)5b; M = Mo, n = 5, Ar = Ph 6; M = W, n = 5, Ar = 4-Me(2)NC(6)H(4)7).
Erscheinungsjahr
2019
Zeitschriftentitel
CHEMICAL SCIENCE
Band
10
Ausgabe
48
Seite(n)
11078-11085
ISSN
2041-6520
eISSN
2041-6539
Page URI
https://pub.uni-bielefeld.de/record/2939927

Zitieren

Rottschäfer D, Blomeyer S, Neumann B, Stammler H-G, Ghadwal R. Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. CHEMICAL SCIENCE. 2019;10(48):11078-11085.
Rottschäfer, D., Blomeyer, S., Neumann, B., Stammler, H. - G., & Ghadwal, R. (2019). Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. CHEMICAL SCIENCE, 10(48), 11078-11085. doi:10.1039/c9sc04441h
Rottschäfer, D., Blomeyer, S., Neumann, B., Stammler, H. - G., and Ghadwal, R. (2019). Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. CHEMICAL SCIENCE 10, 11078-11085.
Rottschäfer, D., et al., 2019. Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. CHEMICAL SCIENCE, 10(48), p 11078-11085.
D. Rottschäfer, et al., “Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides”, CHEMICAL SCIENCE, vol. 10, 2019, pp. 11078-11085.
Rottschäfer, D., Blomeyer, S., Neumann, B., Stammler, H.-G., Ghadwal, R.: Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides. CHEMICAL SCIENCE. 10, 11078-11085 (2019).
Rottschäfer, Dennis, Blomeyer, Sebastian, Neumann, Beate, Stammler, Hans-Georg, and Ghadwal, Rajendra. “Direct functionalization of white phosphorus with anionic dicarbenes and mesoionic carbenes: facile access to 1,2,3-triphosphol-2-ides”. CHEMICAL SCIENCE 10.48 (2019): 11078-11085.
Material in PUB:
Dissertation, die diesen PUB Eintrag enthält