Carbene complexes of iridium, rhodium, manganese, chromium, and iron containing thiazolidinylidene and pyridinylidene ligands

New carbene complexes of IrI, RhI, MnI, Cr0, and Fe0 have been prepared by reactions of the appropriate carbonylmetal anions with N-methyl- and N-ethyl-2-chloro-4-methylthiazolium tetrafluoroborate and N-methyl-2-chloropyridinium tetrafluoroborate. The anions [Ir(CO)3PPh3]–, [Rh(CO)2(PPh3)2]–, and [Mn(CO)5]– afford cationic carbene complexes, whereas [Cr(CO)5]2– and [Fe(CO)4]2– yield neutral carbene complexes. Treatment of [Mn(CO)5{[graphic omitted]}][BF4] with iodide ion gives a neutral complex [cis-Mnl(CO)4{[graphic omitted]}].The cation [Ir(CO){[graphic omitted]}(PPh3)2]+ reacts with hydrogen to give [IrH2(CO){[graphic omitted]}(PPh3)2]+. The cation also reacts oxidatively to give IrIII complexes with HCl, Cl2, and I2. Lithium chloride or bromide reacts to give [IrH(X)(CO){[graphic omitted]}(PPh3)2][BF4](X = Cl or Br), whereas [Ir(CO){[graphic omitted]H}(PPh3)2][BF4] affords the neutral IrIII species [IrCl3{[graphic omitted]H}(PPh3)2]. Methyl iodide reacts with [Ir(CO){[graphic omitted]}(PPh3)2][BF4] to give [Irl2Me(CO){[graphic omitted]}(PPh3)].Some spectroscopic properties of the new complexes are reported.