The manganese salt [C5H5Mn(CO)2NO] [PF6] reacts with various tertiary phosphines and related ligands upon heating in methanol without ultraviolet irradiation to form yellow to orange substitution products [C3H3Mn(CO)(NO)L] [PF6] (L = (C6H5)3P, (C6H5)3As, (C6H5)3Sb, and (C6H3)2PC≣CC6H5 but not (C6H5)3Bi or (C6H5O)3P). The ditertiary phosphine cis-(C6H5)2PCH=CHP(C6H5)2 reacts with [C5H5Mn(CO)2NO] [PF6] to form the red-orange bidentate monometallic (chelate) derivative [C5H5Mn(NO)(diphos)] [PF6]. The other ditertiary phosphines (C6H5)2PCH2CH2P(C6H5)2, trans-(C6H5)2PCH=CHP(C6H5)2, (C6H5)2PC≣CP(C6H5)2, and (C6H5)2PCH2C≣CCH2P(C6H5)2 may form monodentate monometallic derivatives of the type [C5H5Mn(CO)(NO)(diphos)] [PF6] and/or bidentate bimetallic (bridging) derivatives of the type [C5H5Mn-(CO)(NO)]2(diphos)[PF6]2 depending on the ligand and the reaction conditions. The triteriary phosphine CH3C[CH2P-(C6H5)2]3 reacts with [C5H5Mn(CO)2NO] [PF6] to form [(C5H5)2Mn2(CO)(NO)2(triphos)] [PF6]2 in which two of the phosphorus atoms are bonded to one manganese atom and the third phosphorus atom is bonded to the other manganese atom. The infrared and proton nmr spectra of the new compounds are discussed. © 1969, American Chemical Society. All rights reserved.
