B. Denise et al., REACTION OF AMINOCARBENE COMPLEXES OF CHROMIUM AND TUNGSTEN .6. REARRANGEMENTS OF AND INSERTIONS OF ALKYNES INTO AZIRIDINYLCARBENE COMPLEXES, Journal of organometallic chemistry, 494(1-2), 1995, pp. 43-51
yl[(2-methylaziridinyl)(methyl)carbene]chromium(0) (2a) reacts with Li
Bu followed by H2O to regenerate the starting carbene complex. Treatme
nt of the same reaction mixture with D2O leads to the perdeuteromethyl
carbene complex 2D(3). However, addition of CH3I instead of D2O gives
-methyl-2-aza-3-methylcyclopentylidene)chromium(0) (28) by ring openi
ng followed by alkylation at nitrogen. The aziridinylcarbene complexes
[(CO)(5)M = C(NCH(CH3)CH2)R(1)(M = Cr, R(1) = Me, 2a, R(1) = Ph, 2b,
R(1) = cyclopropyl, 2c react with diphenylacetylene or phenylpropyne)
to give 30a-c, 33 and 34 via double alkyne and single CO insertions. H
owever, complex 20 (M = W, R(1) = Me) gave only trace amounts of the e
xpected complex 30d. Treatment of 30a with pyridine led to the metal-f
ree derivative 31. Complex 30b (R(1) = Ph) was fully characterized by
X-ray diffraction.