The nitrosyl dimer [Fe(NO)2Cl]2 (1) in the presence of l,2-bis(diphenylphosphino)ethane (dppe) or tra/u-l,2-bis(diphenylphosphino)ethene (tdppen) yields the binuclear complex [Fe(NO)2Cl]2(^-dppe) (2) or [Fe(NO)2Cl]2fii-tdppen) (6). In the presence of excess diphosphine dppe, tdppen, or cis-1,2-bis(diphenylphosphino)ethene (cdppen), the Fe(NO)2X moiety undergoes (i) halogen displacement to yield Fe(NO)2(PP) complexes of |Fe(NO)2)10 configuration and (ii) unexpectedly, NO substitution, which results in Fe(NO)Cl2(OPP) species of |Fe(NO)|9 configuration, where the diphosphine has been monooxygenated by NO.
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