<jats:title>Abstract</jats:title><jats:p>A facile method for the preparation of N1‐ (<jats:bold>1a–6a</jats:bold>) and N3‐alkylated (<jats:bold>1b–6b</jats:bold>) 4‐azabenzimidazole derivatives is presented. Both isomers were obtained by alkylation of 4‐azabenzimidazole. The isomers were separated, and the preferred formation of the N1‐alkylated derivatives (<jats:bold>1a–6a</jats:bold>) was observed. The C2‐proton in the alkylated benzimidazoles can be exchanged for an iodine atom by treatment with methyl lithium and iodine, leading to N‐alkylated 2‐iodo‐4‐azabenzimidazoles <jats:bold>7a,b</jats:bold> and <jats:bold>8a</jats:bold>. 2,2<jats:sup>′</jats:sup>‐Bis(4‐azabenzimidazole) derivatives <jats:bold>9a,b</jats:bold> and <jats:bold>10a</jats:bold> were isolated as by‐products of the proton–halogen exchange. Treatment of the N1‐ or N3‐methyl‐4‐azabenzimidazoles <jats:bold>1a,b</jats:bold> with methyl lithium and N‐chlorosuccinimide as a chlorine source proceeded to give 2‐chloro‐4‐azabenzimidazoles <jats:bold>11a,b</jats:bold> without formation of the coupling products, but the yield of 2‐chloro‐1‐methyl‐4‐azabenzimidazole <jats:bold>11a</jats:bold> is low (9%) whereas 2‐chloro‐3‐methyl‐4‐azabenzimidazole <jats:bold>11b</jats:bold> has been obtained in reasonable yield (49%). The reaction of 3‐butyl‐2‐iodo‐4‐azabenzimidazole <jats:bold>7b</jats:bold> with [IrCl<jats:sub>2</jats:sub>Cp*]<jats:sub>2</jats:sub> gave the iridium complex <jats:bold>12</jats:bold>, where 3‐butyl‐2‐iodo‐4‐azabenzimidazole is coordinating to the metal center via the N1 atom. The reaction of the N1‐alkylated 4‐azabenzimidazole with chloroacetone gave the corresponding 1‐alkyl‐3‐(2‐oxopropyl)‐4‐azabenzimidazolium chlorides <jats:bold>13–17</jats:bold> in good yields. The chloride counterion was exchanged for a tetrafluoroborate anion for two derivatives leading to compounds <jats:bold>18</jats:bold> and <jats:bold>19</jats:bold>. Carbene complexes were obtained by treatment of 1‐butyl‐3‐(2‐oxopropyl)‐4‐azabenzimidazolium chloride <jats:bold>15</jats:bold> with silver oxide, followed by transmetalation with [AuCl(tht)] or [IrCl<jats:sub>2</jats:sub>Cp*]<jats:sub>2</jats:sub> leading to the gold(I) (<jats:bold>20</jats:bold>) and iridium(III) complexes (<jats:bold>21</jats:bold>) with 1‐butyl‐3‐(2‐oxopropyl)‐4‐azabenzimidazolin‐2‐ylidene ligand. Removal of the 2‐oxopropyl protecting group by treatment with silica gel proceeded in the case of the iridium complex to give complex <jats:bold>22</jats:bold>, possessing an NH,NR‐stabilized carbene ligand, while it failed for the gold(I) complex. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:476–490, 2011; View this article online at <jats:ext-link xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="http://wileyonlinelibrary.com">wileyonlinelibrary.com</jats:ext-link>. DOI 10.1002/hc.20711</jats:p>