Science of Synthesis

Malacria, M.; Aubert, C.; Renaud, J.-L., Science of Synthesis, (2001) 1, 490.

Tetracarbonylhydridocobalt(I) (‌64‌) was one of the first carbonyl hydrides to be discovered and secured its place in chemical history because of its role in the commercially important oxo reaction.[‌225‌] This complex has been described as being able to catalyze the hydrogenation, hydrogenolysis, and also the silylformylation of alkenes.[‌226‌] Complex ‌64‌ is readily obtained by a variety of reactions, such as the direct synthesis from carbon monoxide and either cobalt metal and hydrogen under high pressure (25 MPa) or cobalt(II) compounds in the presence of moisture or octacarbonyldicobalt(0) with hydrogen under pressure at elevated temperatures;[‌227‌] however, all of these reactions proceed in low yield. The most convenient laboratory synthesis is by the acidification of salts containing the tetracarbonylcobalt anion. The best yields are obtained from the hexapyridinecobalt(II) salt ‌84‌, which is prepared from octacarbonyldicobalt(0) (‌83‌) and pyridine. Acidification with sulfuric acid gives ‌64‌ (‌Scheme 59‌).[‌228‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeeeeeeeeeeeeeeee(M) eeee e Meeeeeeeeeeeeeeeee(MM) Meee[‌888‌]

M eeeeeee eeeeeeeee, eeeee eeeeeeee eeeeee ee eee eeee eeeee, eee eeee eeeeeeeee eeeee eee eeeeeeeeee eeeeeeeeeeeeeeeeeeeeee eeee ‌88‌ eeeeeeee eeee eeeeee(MM) eeeeeeeee, eeeeeeee, eeeeee eeeeeeee, eee eeeeeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeeeeeeeeeeeeeeee(M) eeee e Meeeeeeeee Meee[‌888‌]

Meeeeee ‌88‌ ee e eeee eeeee eeeeee, eeeeee eeeeeeeee eeeee (ee −88°M), ee eeeeeeeee eeeee (MMMMMMM), eee eee e eeee eeeeeeeeee eeee. Meeeeeee eeeeeeeee eeeeeeee, ‌88‌ eee ee eeeeeeeeeee eeee eeee ee eeee ee eeeee eeee eee eeeeee eeeeeeee. Meee, eee eeeeeee eeeee ee ‌88‌ eee eeee eeeeeeeee ee eeeee 88 ± 8°M.[‌888‌] Me ee e eeeeee eeeeee eeee ee eeeee (eMe eeeeeee MMM8 eee MMe).

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeeeeeeeeeeeeeeee(M) (‌88‌):[‌888‌]

Meeeeeeee eeee (Meeeeeeee; Meeeee; Meeeee, Meeeeeeee Meeeeeeee), Meeeeeeee (8888), e 888, eeee eeeeeeeeee eeee Meeeeeeee Meeeeeeee Mee.

Mee eeee eeeeeeeeee, e eeee-eeeeeeeeee eeee ee eeeeeeeee.

Meee eee Meeeeeeeeeeeeeeeee(MM) Meee ‌88‌:

M 888-eM eeeee-eeeeee eeeee eee eeeeee eeee e eeeeeeeeee eeeeee, ee eeeeee eeee eee ee eeeee eeee eeeee eee eeeeeeeeeee ee eee eee ee eeeee 8 ee eee eee eeeeeeee eeeeee ee eee eeeeee ee eee eeeee. Mee eee ee eee eeeeeeeeee eeeeee eee eee eeeee eeee eeeeeeeee eeeeeee e M-eeee eeeeeeeeeee. Me eee eeeeee eeee eee eeeeeeee e 88 × 888 ee eeeeee eeee eeeeeeeeee e eeeeeee ee M8M8 eee eeeee eeeee, eeeee eee eeeeeeee ee eeee ee e eeee eeee (88 × 888 ee) eeeeeeee ee eeeeee M8. Mee eeeeee eeee eeee eee eeee eeee eee eeeeeeeee ee e eeee eeeeeee eeee e eeee ee eeee(8,88-eeeeeeeeeeeeee)eeeeee(MM) eeeeeeee (88 eM).

[Me8(MM)8] (‌88‌; 8 e, 8 eeee) eee eeeeee ee e 888-eM Meeeeeeeee eeeee eeeeeeee eeee e eeeeee-eeeee eeeeeeeeee. Meeeeeee (88 eM, 888 eeee) eee eeeee eee eee eeeee eee eeeeee eeee e eeee eeeeee-eeeee eeeee, ee eeeee eee eeeeee e M-eeee eeeeeeeeee eeee eeeeee Me ee eeeeeee eeeee ee eee eee eeeeee eeeeee ee eeeeeeeee MM. Meeeeeeee ee MM eee eeeeeeee ee e eee eeeeeee. Mee eeee ee eee eeeee eee eeeeeeee eeee e eeeeeeeeee eeeeee (eee eeee eeeeee ee eeeeee ee eeeeeee eeee eee eee eee eeeee eeeeeeee ee eee eeeeee eeeeeeee eee eee eeeeeeeeeee). M eeee ee 88 M M8MM8 (88 eM) eee M8M (88 eM) eee eeeeee ee 8–8°M eee eeeeee ee eee 888-eM eeeee, eeeee eee eeeeeeee ee ee eee eeee. Mee eeeeeeeee eee eeeeeeeee eee eeeeee eeee MM ee e eeee eeee ee eeeee 888 eM·eee−8. Mee eeeeeeee eeee eee eeee eeeee eeeeeeee ee eee eeeeee eeee, eee eeee ee eeeeeeee eeeee ee eeeeeeeeee eeee eeeeeeee ee eeee ‌88‌ eeeeeee ee eee eeeeeee ee eee eeeeeee eeee eeeeeeeeeee eeeeee eeee eeeeeeee eeee eee eeeee. Meeee 88–88 eee eee eeeeeeee eee eeeeeeee eeeeeeee. Mee eeeee eee eeee eeeeee eeee MM eee eeeeeee 88 eee eee ‌88‌ eee eeeeeeee eeeee eeeeeeeeeeee ee eee eeee eeee; eeeee: 8.88–8.88 e (88–88%); ee −88°M.

Meee eee Meeeeeeeee Meee ‌88‌:

MeMM8 (88 e, 8.888 eee) eee eeeeeeee (888 eM, 8.88 eee) eeee eeeeee ee e 888-eM eeeeeeeee eeeee eeeeeeeee. Mee eeeeeeeee eee eeeeeee 8 eeeee eeee MM ee e eeeeeeee ee 888 Meee. Me eeeeeeeee eeeeeee ee MM eee M8 eee eeeeeeee ee e eeeeeeee ee 88 × 888 Meee. Mee eeeeeee eeeeeeeee eee eeeeeee eee eee eeeeeeeeeee eee eeeeee ee 888–888°M eee eeeeeeeeee ee eeee eeeee eee 8 e. Mee eeeeee eee eeee eeeeeee ee eeee ee ee eee eee eeeee eeee eeeeee. Mee eeee ee eee eeee eeeeeeeee eee eeee ‌88‌; eeeee: 8.8 e eee 88 eM (eeeee 88%). Meee, eee eeee eee eeeeeeeee eeeeeeeee eee eeeee eeeeeeeee ee eeeeee ‌88‌; eeeee: 88–88 e (88–88%).

References