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

Oxo(tert‐butylimido) or bis(tert‐butylimido)osmium(VI) porphyrins Os(Por)(O)( NBu t ) and Os(Por)(NBu t )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)(H 2 NBu t )n (Por=TPP, 4‐C1‐TPP], depending on whether text ‐butylamine is present. The bis( tert ‐butylamine)ruthenium(II) porphyrins [Ru(Por)(H 2 NBu t )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 1 H NMR, UV‐Visible and IR spectroscopy. The X‐ray crystal structures of Os(TTP)(O)(NBu t ).EtOH and Os(4‐Cl‐TPP)(NBu t ) 2 have been determined. Crystal data: for Os(TTP)(O)(NBu').EtOH: monoclinic, space group P2 1 /c, a=1.3546(6) nm, b=2.3180(3) am, c=1.6817(3) nm, β=90.84(2)°, V=527.97(1) nm 3 , Z=4. The Os=O and Os=NBu t distances in Os(TTP)(O)(NBu t ).EtOH are 0.1772(7) nm and 0.1759(9) nm, respectively. The average Os=NBu t distance of Os(4‐C1‐TPP)(NBu t ) 2 is 0.1775 nm.