Transition-metal chemistry of dichloromethylene(dimethyl)ammonium chloride; C-chlorocarbene complexes

Abstract

BN1 9Q J) Summary C-Chlorocarbene d6 complexes of CrO, MnI, and IZhnI, (I)-(V), have been obtained from [Me,NCCl,]+Cland the appropriate transition metal complex precursor, by four procedures (a, a', a", or b) ; alternative reaction pathways (c or d ) lead to other species, including the electron-rich cluster compound [Co,(CO),CNMe,].

Transition-metal dihalocarbene complexes

“…Chloro(dimethylamino)carbene complexes can, in several instances, be formed by transfer of the C(C1)-NMe2 fragment from the iminium salt [Me2N= CC12]+C1-. 93 Three fragment oxidative addition to a rhodium complex yields the chloroaminocarbene as in eq 42. A second complex, RhCl(=C(Cl)NMe2)(PPh3)2, is formed similarly from RhCl(PPh3)3.…”

“…A second mechanism is nucleophilic attack on the salt by a metal anion, producing Mn(=C(Cl)NMe2)(CO)6 from [Mn-(CO)5]~a nd the chromium example shown in eq 43. 93 [ (42) [Cr(CO)5]2-+ [Me2N=CCl2]Cl -Cr(=C(Cl)NMe2)(CO)5 + 2C1" (43) 5. Metalloporphyrln Monohalocarbene Complexes…”