Cationic Carbonyl complexes of manganese(I) with diphosphines |
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| Authors: | G.A. Carried V. Riera |
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| Affiliation: | Department of Inorganic Chemistry, University of Valladolid, Valladolid Spain |
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| Abstract: | The bromo-carbonyls fac-BrMn(CO)3(diphos)(diphos Ph2P(CH2)nPPh2 for n = 1(dpm), 2(dpe), 3(dpp) and 4(dbp)) react with AgClO4 in dichloromethane solution to give the neutral fac-O3ClOMn(CO)3(diphos). The reaction of the latter complexes at room temperature with a variety of ligands L phosphines (PR3), phosphites (P(OR)3), pyridine (Py), acetonitrile (MeCN), tetrahydrothiophene (THT) or acetone (Me2CO) leads to the cationic species fac-[Mn(CO)3(diphos)L]ClO4 (or to the [Mn(CO)4(diphos))]ClO4, when L CO). When L is a phosphorus ligand, the cationic fac-tricarbonyls isomerize upon heating to the mer isomers, which could only be isolated by this method for diphos dpm, the reaction being accompanied by decomposition in the other cases. UV irradiation of the mer-[Mn(CO)3(diphos)L]ClO4 in the presence of a large excess of L gives the corresponding trans-[Mn(CO)2(diphos)L2]ClO4. |
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