Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]

Weber L, Dembeck G, Stammler H-G, Neumann B, Schmidtmann M, Müller A (1998)
Organometallics 17(24): 5254-5259.

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Reaction of the carbyne complexes Tp'(CO)(2)M=C-P=C(NR2)(2) (1, 2) [Tp' = HB(3,5-Me2C3HN2)(3); M = Mo (1, 3); W (2, 4); R = Me (a); Et (b)] with methyl trifluorornethanesulfonate afforded the orange-red salts [Tp'(CO)(2)M=C-P(Me)C(NR2)(2)]SO3CF3 (3, 4), the cations of which can be considered as methylphosphines featuring additional bisaminocarbenium- and metallaalkynyl substituents. Analogously, complex Tp'(CO)(2)W=C-P=C(NEt2)(2) (2b) was protonated with ethereal HBF4 in ether at the phosphorus atom to give [Tp'W=C-P(H)-C(NEt2)(2)]BF4 (5), which in CH2Cl2 solution experienced a clean rearrangement to the metallaphosphirene [Tp'(CO)(2)W=C(H)PC(NEt2)(2)]BF4 (6) Treatment of 2b with F3CSO3H led directly to [Tp'(CO)(2)W=C(H)-PC(NEt2)(2)]SO3CF3 (6'). The molecular structures of 4b and 6' were established by X-ray structure analysis.
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Weber L, Dembeck G, Stammler H-G, Neumann B, Schmidtmann M, Müller A. Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]. Organometallics. 1998;17(24):5254-5259.
Weber, L., Dembeck, G., Stammler, H. - G., Neumann, B., Schmidtmann, M., & Müller, A. (1998). Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]. Organometallics, 17(24), 5254-5259.
Weber, L., Dembeck, G., Stammler, H. - G., Neumann, B., Schmidtmann, M., and Müller, A. (1998). Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]. Organometallics 17, 5254-5259.
Weber, L., et al., 1998. Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]. Organometallics, 17(24), p 5254-5259.
L. Weber, et al., “Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]”, Organometallics, vol. 17, 1998, pp. 5254-5259.
Weber, L., Dembeck, G., Stammler, H.-G., Neumann, B., Schmidtmann, M., Müller, A.: Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]. Organometallics. 17, 5254-5259 (1998).
Weber, Lothar, Dembeck, Gottfried, Stammler, Hans-Georg, Neumann, Beate, Schmidtmann, Marc, and Müller, Achim. “Protonation and Alkylation Reactions at Phosphaalkenyl Carbyne Complexes Tp'(CO)2M≡C-P=C(NR2)2 [Tp' = HB(3,5-Me2C3HN2)3; M = Mo, W; R = Me, Et]”. Organometallics 17.24 (1998): 5254-5259.
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