Abstract
The salt fac-[Mn(CO)3(MeCN)3]PF6 has been prepared by heating under reflux [Mn(CO)5Br] in acetonitrile. It rapidly undergoes substitution of the acetonitrile groups with phosphines and phosphites (L) to give the species fac-[Mn(CO)3L(MeCN)2]+, fac-[Mn(CO)3L2(MeCN)]+, cis-[Mn(CO)2L2(MeCN)2]+, and mer-cis-[Mn(CO)2L3(MeCN)]+ under varying reaction conditions. These cations are also formed on treating the complexes [Mn(CO)5–xLxBr](x= 1–3) with AgPF6 in acetonitrile. The dicarbonyl cations cis-[Mn(CO)2{P(OMe)2Ph}2(MeCN)2]+ and mer-cis-[Mn(CO)2L3(MeCN)]+ are oxidised by NOPF6 to give trans-[Mn(CO)2{P(OMe)2Ph}2(MeCN)2]2+ and mer-trans-[Mn(CO)2L3(MeCN)]2+[L = P(OMe)2Ph and P(OMe)3]. Hydrazine reduction of the cation mer-trans-[Mn(CO)2{P(OMe)3}3(MeCN)]2+ gives mer-trans-[Mn(CO)2{P(OMe)3}3(MeCN)]+ which reacts further with P(OMe)3 to give trans-[Mn(CO)2{P(OMe)3}4]+. 1H N.m.r. resonances of the nitrile methyl groups exhibit some unusual features which are discussed, together with steric factors governing the reactions.
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