Polyhedron
Polyhedron
4 years ago

Synthesis and crystal structures of dimetal tetramethyltetraazaannulene compounds of Rh(I) and Ir(I, II): [(tmtaa)Rh2(COD)2], [(tmtaa)Ir2(CO)4], and [(tmtaa)Ir2(CO)4I2]

Synthesis and crystal structures of dimetal tetramethyltetraazaannulene compounds of Rh(I) and Ir(I, II): [(tmtaa)Rh2(COD)2], [(tmtaa)Ir2(CO)4], and [(tmtaa)Ir2(CO)4I2]
High yield syntheses of [(tmtaa)M2(CO)4] from [(tmtaaH)M(COD)] and [M2(COD)2(μ-OH)2] and CO, in toluene are described (tmtaa=6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine). Crystal structures of the d8–d8 dimetal compounds [(tmtaa)M2(COD)2], M=Rh, and [(tmtaa)Ir2(CO)4] and the d7–d7 [(tmtaa)Ir2(CO)4I2] resulting from oxidative addition of I2 to [(tmtaa)Ir2(CO)4] are analyzed relative to the distortion within the macrocyclic ligand as the M−M bond order increases from zero to one. The oxidative addition reactions of MeI, PhSSPh, and pySSpy to [(tmtaa)Ir2(CO)4] are also described.

Publisher URL: www.sciencedirect.com/science

DOI: S0277538717305016

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