TRANSITION-METAL SILYL COMPLEXES .37. REACTION OF ANIONIC SILYL, GERMYL, AND STANNYL COMPLEXES [(ETA-5-C5H4ME)(CO)2MNSIR3]-, [(ETA-5-C5H4ME)(CO)2MNGER3]-, [(ETA-5-C5H4ME)(CO)2MNSNR3]- WITH GEMINAL ORGANIC DIHALIDES - A NOVEL ROUTE FOR THE PREPARATION OF CARBENE COMPLEXES

The anionic complexes Na[MeCp(CO)2MnER3] (E = Si, Ge, Sn) (MeCp = eta-5-C5H4Me), obtained by deprotonation of the corresponding hydrido complexes MeCp(CO)2Mn(H)ER3, react with 3,3-dichlorocyclopropenes to give the cyclopropenylidene complexes MeCp(CO)2Mn = C-CR = CR (2) by NaCl and R3ECl elimination. Aminocarbene complexes MeCp(CO)2Mn = C(NR2)R' (5), including the N-methylpyridinylidene complex MeCp(CO)2Mn = CN(Me)CHCHCHCH (5h) and a thiazolinylidene derivative, MeCp(CO)2Mn = CN(Me)C(Me)CHS (5i), were alalogously prepared from [MeCp(CO)2MnSiMePh2]- and [R2N = C(R')Cl]+. In these reactions, the anionic complexes Na[MeCp(CO)2MnER3] act as preparative equivalents to the dianionic complex MeCp(CO)2Mn2-. The X-ray structure analysis of 5i is reported (Mn-C(carbene) 197.0 (3) pm): monoclinic, space group P2(1)/c (Z = 4), a = 736.4 (1) pm, b = 1418.4 (3) pm, c = 1304.6 (1) pm, beta = 95.58 (1)-degrees.