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A cyclometalated N-heterocyclic carbene: the wings of the first Pt2 (II,II) butterfly oxidized by CHI3

AuthorsArnal, Lorenzo; Fuertes, Sara ; Martín, Antonio ; Baya, Miguel ; Sicilia, Violeta
KeywordsBridging pyrazolate
Cyclometalated NHC
Dinuclear PtIII
Molecular butterfly
Oxidative addition
Issue Date2018
CitationChemistry - A European Journal 24(70): 18743-18748 (2018)
AbstractThe X-ray study on a single crystal of the butterfly-like complex [{Pt(C^C*)(μ-pz)}2 ] (1), containing a cyclometalated N-heterocyclic carbene ligand as wings (HC^C*=1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene), showed three molecules in the asymmetric unit with intermetallic separations (Å) of 3.2294(4) (1A), 3.2834(4) (1B), and 3.1208(6) (1C). From the reaction of 1 with excess of CHI3 in the air and the sunlight, complex [{Pt(C^C*)(μ-pz)I)}2 ] (2) (dPt-Pt =2.6079(2) Å) was obtained as the major product, while [IPt(C^C*)(μ-pz)2 Pt(C^C*)CHI2 ] (3) (dPt-Pt =2.6324(3) Å) was obtained as the major product under argon atmosphere in the dark. Experimental and theoretical investigations showed that an easily accessible radical-like mechanism operates under thermal conditions, with dioxygen acting as an efficient radical (R. ) scavenger. The oxidation of a Pt2 (II,II) "butterfly" by CHI3 to give metal-metal bonded Pt2 (III,III) compounds is described now for the first time.
DescriptionDedicated to Professor Ernesto Carmona on the occasion of his 70th birthday.
Publisher version (URL)https://doi.org/10.1002/chem.201804013
Appears in Collections:(ISQCH) Artículos
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