Synthesis of copper(I) bis(3,5-dimethylpyrazolyl)methane olefin complexes and their reactivity towards carbon monoxide

The chemistry of bis(3,5-dimethylpyrazolyl)methane complexes of copper(I) has been investigated and a dinuclear copper(I) derivative of formula {Cu2[μ-CH2(3,5-Me2Pz)2]2}(TfO)2 [TfO = trifluoromethanesulphonate anion, CF3SO3-], characterized by an uncommon bridging coordination of the bis(pyrazolyl)methane ligands, has been isolated and characterized by X-ray diffraction methods. Moreover, new olefin derivatives of general formula [Cu[CH2(3,5-Me2Pz)2](olefin)]TfO have been prepared (olefin: coe = cyclooctene, van = 4-vinylanisole, nbe = norbornene), their carbonylation reactions, {Cu[CH2(3,5-Me2Pz)2](olefin)}TfO + CO ⇆ {Cu[CH2(3,5-Me2Pz)2](CO)}TfO + olefin, have been studied gas volumetrically and the thermodynamical parameters of the equilibria for the displacement of the coordinated olefin by carbon monoxide have been determined.

Graphical abstractNew copper(I) bis(3,5-dimethylpyrazolyl)methane complexes have been prepared, the carbonylation reactions of new olefin derivatives of general formula [Cu[CH2(3,5-Me2Pz)2](olefin)]TfO have been studied and the parameters of the equilibria for the displacement of the coordinated olefin by carbon monoxide – {Cu[CH2(3,5-Me2Pz)2](olefin)}TfO + CO ⇆ {Cu[CH2(3,5-Me2Pz)2](CO)}TfO + olefin – have been determined.Figure optionsDownload full-size imageDownload as PowerPoint slide