A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

Abstract

Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction. In a first step, DMF‐containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl species in the same oxidation state are obtained, presumably as a result of HCl‐mediated DMF decomposition. Provided that water levels are kept low, reduction can occur to provide the complexes [NH2(CH3)2][RhCl2(CO)2], [NH2(CH3)2][RuCl3(CO)2(DMF)], [RuCl2(CO)2(DMF)2], and [NH2(CH3)2][IrCl2(CO)2]. In the case of platinum, reduction is not effective and [NH2(CH3)2][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesized in this way, the reaction producing copious amounts of colloidal metal. Adding phosphanes to these chlorocarbonyl‐containing solutions allows easy, one‐step syntheses of a variety of complexes.

Mono- and double carbonylation of iodobenzene in the presence of reusable supported palladium catalysts

“…Palladium was immobilised using different precursors ( Table 1) and solvents. Pd(II) compounds may be reduced to catalytically active Pd(0) during the aminocarbonylation reaction with the help of CO [30], Et 3 N [31], or by the solvent (e.g., DMF [32]). In the case of CAT-2/2 -CAT-2/4 heterogenisation was carried out in EtOH to facilitate reduction of Pd(II) to Pd(0) [33] prior to carbonylation.…”

Ruthenium(II) arene complexes with oligocationic triarylphosphine ligands: Synthesis, DNA interactions and in vitro properties

“…the tendency of the Ru-phosphine complex to undergo aquation. There is no clear correlation between the extent of aquation of these complexes and the basicity of the corresponding phosphine ligands, which have the following order of decreasing basicity, determined through the frequency of the CO stretching vibration in the IR spectrum of complexes of the type trans-RhCl (CO)L 2 (L ¼ monodentate phosphine ligand): pta (1963 cm À1 ) [33] >tppts (1968 cm À1 ) [34] >1a (1971 cm À1 ) [18] >2a (1981 cm À1 ) [18]. With the negatively charged phosphine in 5, extensive and rapid aquation is observed and at the other extreme, for 2b which contains a hexacationic phosphine ligand, aquation is not observed.…”

Microwave‐Acceleratedmetal Catalysis: Organic Transformations at Warp Speed

“…In similarity to DMF, formamide is known to undergo thermal decomposition. However, formamide simultaneously generates both ammonia and carbon monoxide 77 . Therefore formamide was selected as a suitable combined solvent, ammonia synthon and CO source for the synthesis of primary benzamides.…”

“…presents two selected examples from the reported results77 where imidazole was used as an essential activating agent. Good isolated yields were demonstrated with different types of aryl bromides after only 400 s In situ aminocarbonylation with DMF as the carbon monoxide source.Scheme 2.35In situ aminocarbonylation with formamide as a combined carbon monoxide and ammoniareleasing solvent.…”