The Chemistry of Metal Carbonyls. III. The Reaction between Dicobalt Octacarbonyl and Dimethylamine¹

Abstract

The polyiodide ions mentioned here have been encountered by previous investigators in both inorganic and organic solids. Thus, for example, compounds represented by the formulas 3• 20, Rbl3, KI7-H20 and KI9-3C6H6 have been isolated.JS In addition, organic compounds containing the triiodide, heptaiodide or enneaiodide ion have also been mentioned in the literature. As examples of these we have the compounds (CH3)4NI3,19 (C2H5)4PI3,20 (C2H6)R4NI719a and (CH3)4NI9.19•21

Nitrogen-Containing Systems

“…These reactions are catalysed by carbonyl complexes of iron, cobalt, nickel, palladium, manganese, rhodium and ruthenium [19][20][21][22][23][24][25] .…”

“…For example, secondary aliphatic and heterocyclic amines, such as piperidine, are selectively converted to the corresponding N-formyl derivatives (Reaction 30) in the presence of CO 2 (CO)s [20] or RU3(CO)12 [21,22] as catalysts. In the latter case the reaction proceeds under relatively mild conditions (75°C and 1 bar).…”

“…The active catalyst in these reactions is probably the metal carbonylate anion, formed by reaction of the metal carbonyl with the amine. For example,C0 2 (CO)s reacts with dimethylamine by the following disproportionation reaction [20] : When a high pressure of CO is employed catalytic carbonylation is observed [20] . The key intermediate in these reactions is assumed to be a carbamoylmetal species (R2 NCOM).…”

Formylation of Amines by Dimethylformamide in the Presence of Hydrous Zirconium Oxide

“…Catalytic carbonylation of amines, l -4) a reaction of amines with formic acid derivatives,S) and amide-interchange reactions between amines and arriides 6 ) have been reported for formylation. N'-Formylnornicotine (2) is an intermediate for the conversion of nornicotine (1) …”

Formylation of amines by dimethylformamide in the presence of hydrous zirconium oxide.

“…Catalytic carbonylation of amines,1~4) a reaction of amines with formic acid derivatives,5} and amide-interchange reactions betweenamines and amides6) have been reported for formylation. W-Formylnornicotine (2) is an intermediate for the conversion of nornicotine (1) …”