L. Weber et al., Protonation and alkylation reactions at phosphaalkenyl carbyne complexes Tp '(CO)(2)M C-P = C(NR '(2))(2) [Tp ' = HB(3,5-Me2C3HN2)(3), M = Mo, W, R = Me, Et], ORGANOMETAL, 17(24), 1998, pp. 5254-5259
Reaction of the carbyne complexes Tp'(CO)(2)M=C-P=C(NR2)(2) (1, 2) [Tp' = H
B(3,5-Me2C3HN2)(3); M = Mo (1, 3); W (2, 4); R = Me (a); Et (b)] with methy
l 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 meth
ylphosphines featuring additional bisaminocarbenium- and metallaalkynyl sub
stituents. Analogously, complex Tp'(CO)(2)W=C-P=C(NEt2)(2) (2b) was protona
ted 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 rearrange
ment to the metallaphosphirene [Tp'(CO)(2)W=C(H)PC(NEt2)(2)]BF4 (6) Treatme
nt 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 struc
ture analysis.