CHEMISTRY OF [(ETA(6)-C6H5OH)MN(CO)(3)]BF4 - SYNTHESIS OF DISUBSTITUTED CYCLOHEXADIENYLMANGANESE COMPLEXES FROM (C6H5O)MN(CO)(2)L (L=CO, PPH(3), P(OME)(3))

Abstract

Treatment of [(eta(6)-phenol)Mn(CO)(3)](+) (1(+)) with t-BuOK led to [(eta(5)-C6H5O)Mn(CO)(3)] [2(CO)]. Treatment of 1(+) with NMO or TMANO (1 equiv) and PR(3) (3 equiv) led to the oxocyclohexadienyl complex [(eta(5)-C6H5O)Mn(CO)(2)PR(3)] [2(PR(3)) (R = Ph, OMe)]. 2(L) reacts consecutively with a nucleophile (Nu) and an electrophile (E) to give reasonable to high yields of double-addition products, [{6-Nu-eta(5)-1-EO-C6H5}Mn(CO)(2)L] (3) (L = CO, PPh(3), P(OMe)(3)). Demetalation of 3 by using Jones reagent resulted in a high yield of ortho-disubstituted arenes. X-ray crystallographic studies of 2(CO), 2(PPh(3)), and 3(L = P(OMe)(3), Nu = Ph, E = C(O)CH3) have been determined.