Neutral and cationic dicarbonyl complexes of manganese (I) with diphosphines |
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| Authors: | G.A. Carriedo V. Riera J. Santamaria |
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| Affiliation: | Department of Inorganic Chemistry, University of Valladolid Spain |
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| Abstract: | The reaction of BrMn(CO)5 with dppm in refluxing toluene gives the neutral compunds cis-cis-BrMn(CO)2(dppm)2 which has been shown by 31P NMR spectroscopy to have one dppm monodentate and the other bidendate. This complex reacts with TIPF6 in dichloromethane solution to give the salt cis-[Mn(CO)2-(dppm)2]PF6 or, if the reaction is carried out in the presence of CO, the salt mer-[Mn(CO)3(dppm)2]PF6 which also has one monodentate dppm (by 31P NMR). The cationic complex cis-[Mn(CO)2(dppm)2]+ isomerizes to the transisomer when irradiated with UV light, while heating of the latter gives back the cis-isomer. The perchlorate salts of the cation cis-[Mn(CO)2(dppm)2+ can be prepared by reacting fac-O3ClOMn(CO)3(dppm) withdppm in refluxing toluene, and trans-[Mn(CO)2(diphos)(diphos)′]+, diphos or diphos′ being dppm or dppe, by treating the fac-O3ClMn(CO)3(diphos) with dppm or dppe under UV irradiation. |
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