XXXVIII.—Cuprous formate

Mass Spectral Studies of Binuclear Metal Complexes: Copper(I) Carboxylates

“…only slightly smaller than 180". This structure is I in accord with the known preference for Cu (1) ..\ -;C-R in the aqueous solution chemistry of copper. Since the pioneering work of Shannon and coworkers (19,31), many correlations between mass spectral fragmentation patterns and the relative stabilities of metal oxidation states have been made (ref.…”

“…While monitor-classification for the compounds of Tables 1 and Can (22). We obtained residues in all cases (except for the chloroacetates for which volatile copper-(I) chlorides can be formed (Table 1)) indicating, at best, only partial conversion to copper (1) carboxylates for the compounds of Table 2.…”

“…Only a few copper(1) carboxylates have been prepared by simple methods (9,10). However, our initial observations (1 1) that copper(1) acetate and benzoate could be produced thermally from the corresponding copper-(11) complexes prompted a search for other copper (1) carboxylates that could be detected in a similar way. Consequently, we prepared twentyfive copper(I1) carboxylates and in eleven cases were able to detect volatile copper(1) carboxylates among the products of decomposition of a sample of the copper(I1) compound heated on the sample probe of a mass spectrometer.…”

“…Since the reports of the synthesis of copper (1) I formate and acetate near the beginning of this century (1-3) the structures and chemistry of 1 copper(1) carboxylates have, until recently, been \ largely ignored. It is now apparent that compounds of this class may be useful reagents, particularly for organic synthesis.…”

“…For example, synthesis of thiolbenzoate esters can be achieved with copper(1) thiobenzoate (4). Some copper (1) carboxylates can be decarboxylated giving organocopper intermediates which may then be coupled with aryl halides to give unsymmetrical biaryls, oxidized or pyrolyzed to give symmetrical biaryls, or hydrolyzed to arenes (5)(6)(7)(8). Knowledge as to the relative stabilities and properties of copper(1) carboxylates would be useful in their synthesis and characterization.…”