Alkylimido osmium(VI) and ruthenium(VI) porphyrins. Crystal and molecular structures of Os(TTP)(O)(NBut)‐ EtOH and OS(4‐C1‐TPP)(NBut)2

Oxo(tert‐butylimido) or bis(tert‐butylimido)osmium(VI) porphyrins Os(Por)(O)( NBut) and Os(Por)(NBut)2, [Por=meso‐tetrakis(p‐tolyl)porphyrinato (TTP) and meso‐tetrakis(4‐chlorophenyl)porphyrinato (4‐CI‐TPP)] were synthesized by air oxidation of bis(tert‐butylamine)osmium(II) porphyrins [Os(Por)(H2NBut)n (Por=TPP, 4‐C1‐TPP], depending on whether text‐butylamine is present. The bis(tert‐butylamine)ruthenium(II) porphyrins [Ru(Por)(H2NBut)z, Por=TTP, 4‐CI‐TPP] can undergo bromine oxidation to give oxo(tert‐butylimido)ruthenium(VI) complexes in quantitative yields. All these nem complexes were characterized by 1H NMR, UV‐Visible and IR spectroscopy. The X‐ray crystal structures of Os(TTP)(O)(NBut).EtOH and Os(4‐Cl‐TPP)(NBut)2 have been determined. Crystal data: for Os(TTP)(O)(NBu').EtOH: monoclinic, space group P21/c, a=1.3546(6) nm, b=2.3180(3) am, c=1.6817(3) nm, β=90.84(2)°, V=527.97(1) nm3, Z=4. The Os=O and Os=NBut distances in Os(TTP)(O)(NBut).EtOH are 0.1772(7) nm and 0.1759(9) nm, respectively. The average Os=NBut distance of Os(4‐C1‐TPP)(NBut)2 is 0.1775 nm.