The sluggish oxidants, [FeIV(O)(TMC)(CH3CN)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and [FeIV(O)(d12-TMCN)(OTf)]+ (3d; d12-TMCN = 1,4,7,11-tetra-d3-methyl-1,4,7,11-tetraazacyclotetradecane), are transformed into a highly reactive oxidant, [FeIV(O)(TMCO)(OTf)]+ (1; TMCO = 4,8,12-trimethyl-1-oxa-4,8,12-triazacyclotetradecane), upon replacement of a -NMe donor in the TMC and TMCN ligands by an O-atom. A rate enhancement of 5 – 6 orders of magnitude in both H-atom and O-atom transfer reactions is observed upon oxygen incorporation into the macrocyclic ligand and can be explained based upon the higher electrophilicity of the iron center and the higher availability of the more reactive S = 2 state in 1. This rationalizes nature’s preference for using O-rich ligand environments for the hydroxylation of strong C-H bonds in enzymatic reactions.

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The reaction of a terminal alkyne (RCCH) and an aniline (R 0 C 6 H 4 NH 2 ) with the dinuclear species [Cp*IrCl 2 ] 2 afforded cyclometalated amino-carbene derivatives Cp*Ir(Cl)[dC(CH 2 R)NHC 6 H 3 R 0 ] via a hydroamination and an orthometalation. The reaction pathway has been examined through deuterium labeling and computational studies.

[Cp*IrCl2]2 catalyzes the cyclization of 2-ethynylanilines to 2,2'-biindoles via intramolecular hydroamination. A reaction pathway has been proposed on the basis of deuterium labeling experiments and computational studies.

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