Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W)

Weber L, Meyer M, Stammler H-G, Neumann B (2001)
Chemistry - a European Journal 7(24): 5401-5408.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
The reaction of the arylated Fischer carbene complexes [(CO)(5)M=C(OFt)Ar] (Ar = Ph; M=Cr, W, 2-MeC6H4; 2-MeOC6H4, M = W) with the phosphaalkenes RP C(NMe2)(2) (R=tBu, SiMe3) afforded the novel phosphaalkene complexes [{RP=C(OEt)Ar}M(CO)(5)] in addition to the compounds [{RP-C(NMe2)(2)}M(CO)(5)]. Only in the case of the R = SiMe3 (E/Z) mixtures of the metathesis products were obtained. The bis(ditnethylamino)-methylene unit of the phosphaalkene precursor was incorporated in olefins of the type (Me2N)(2)C=C(OEt)(Ar). Treatment of [(CO)(5)W=C(OEt)(2-MeOC6H4)] with HP=C(NMe2)(2) gave rise to the formation of an E/Z mixture of [{(Me2N)(2)CH-P=C(OEt)-(2-MeOC6H4)}W(CO)(5)] the organophosphorus ligand of which formally results from a combination of the carbene ligand and the phosphanediyl [P-CH(NMe2)(2)]. The reactions reported here strongly depend on an inverse distribution of pi -electron density in the phosphaalkene precursors (P-delta-C-delta+), which renders these molecules powerful nucleophiles.
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Chemistry - a European Journal
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7
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24
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5401-5408
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Weber L, Meyer M, Stammler H-G, Neumann B. Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W). Chemistry - a European Journal. 2001;7(24):5401-5408.
Weber, L., Meyer, M., Stammler, H. - G., & Neumann, B. (2001). Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W). Chemistry - a European Journal, 7(24), 5401-5408. doi:10.1002/1521-3765(20011217)7:24<5401::AID-CHEM5401>3.0.CO;2-D
Weber, L., Meyer, M., Stammler, H. - G., and Neumann, B. (2001). Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W). Chemistry - a European Journal 7, 5401-5408.
Weber, L., et al., 2001. Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W). Chemistry - a European Journal, 7(24), p 5401-5408.
L. Weber, et al., “Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W)”, Chemistry - a European Journal, vol. 7, 2001, pp. 5401-5408.
Weber, L., Meyer, M., Stammler, H.-G., Neumann, B.: Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W). Chemistry - a European Journal. 7, 5401-5408 (2001).
Weber, Lothar, Meyer, Marco, Stammler, Hans-Georg, and Neumann, Beate. “Reactivity of the inversely polarized phosphaalkenes RP=C(NMe2)(2) (R = tBu, Me3Si, H) towards arylcarbene complexes [(CO)(5)M=C(OEt)Ar] (Ar = Ph, M = Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M = W)”. Chemistry - a European Journal 7.24 (2001): 5401-5408.

3 Zitationen in Europe PMC

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Facile rotation around a silicon-phosphorus double bond enabled through coordination to tungsten.
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