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

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Abstract
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.