Reaction of cis-bis[1,2-bis(dimethylphosphino)ethane]dicarbonyl-chromium and -molybdenum complexes with silver(I) salts. Reduction of nitrite ion to dinitrogen oxide
- 1 January 1979
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1231-1237
- https://doi.org/10.1039/dt9790001231
Abstract
The complexes cis-[M(CO)2(dmpe)2](M = Cr or Mo; dmpe is Me2PCH2CH2PMe2) undergo one-electron oxidation by Ag[BF4] in solution to give paramagnetic complexes trans-[M(CO)2(dmpe)2][BF4]. Oxidation of cis-[Mo(CO)2(dmpe)2] with silver(I) salts of co-ordinating anions AgnX (n= 1, X =[NCS]–, [NO3]–, or [NO2]–; n= 2, X =[CO3]2– or [SO4]2–) produces the seven-co-ordinate molybdenum(II) complexes cis-[MoX(CO)2(dmpe)2]X (X = NCS or NO3), [MoX(CO)(NO)(dmpe)2](X = NO2), and zwitterions cis-[Mo(OZOm)(CO)2(dmpe)2](Z = C, m= 2; Z= S, m= 3). Photolysis of cis-[Mo(OSO3)(CO)2(dmpe)2] gives [Mo(O2SO2)(CO)(dmpe)2]. The mechanisms of the elimination reactions are discussed and comparisons are made with the reactions of some isoelectronic systems. Disproportionation of molybdenum(I) in trans-[Mo(CO)2(dmpe)2]+ ion is recognised as an important feature of certain oxidations.Keywords
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