Relativistic and nonrelativistic density functional theory calculationswere used to investigate rare or nonexistent ruthenium and osmium analogues ofnitrosylhemes. Strong ligand field effects and, to a lesser degree, relativistic effectswere found to destabilize {RuNO}7 porphyrins relative to their {FeNO}7analogues. Substantially stronger relativistic effects account for the even greaterinstability and/or nonexistence of {OsNO}7 porphyrin derivatives.
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