SIMPLIFIED IN SITU SYNTHESES OF ANHYDROUS PENTACARBONYLHYDROMANGANESE

Three rapid, convenient procedures are reported for the in situ preparation of anhydrous HMn(CO)/sub 5/ in tetrahydrofuran (THF). Protonation of Li(Mn(CO)/sub 5/) in situ previously prepared by the reaction of Mn/sub 2/(CO)/sub 10/ with Li(C/sub 2/H/sub 5/)BH in THF yielded HMn(CO)/sub 5/ which was contaminated by (C/sub 2/H/sub 5/) from the preparation and by Li/sup +/CF/sub 3/SO/sub 3//sup -/ from the protonation reaction by trifluormethanesulfonic acid (CF/sub 3/SO/sub 3/H). HMn(CO)/sub 5/ free from (C/sub 2/H/sub 5/)/sub 3/B can be prepared by volatilizing the (C/sub 2/H/sub 5/)/sub 3/B along with the solvent, or alternately, the (Mn(CO))/sup -/ can be isolated as its crystalline ..mu..-nitrido-bis-(triphenylphosphorous) salt. The in situ synthesis of HMn(CO)/sub 5/ free from ionic byproducts was accomplished by the solvolysis in methanol of (CH/sub 3/)/sub 3/Si(Mn(CO)/sub 5/).