A Cyclometalated N-Heterocyclic Carbene: The Wings of the First Pt 2 (II,II) Butterfly Oxidized by CHI 3

The X-ray study on a single crystal of the butterfly-like complex [{Pt(C^C*)(μ-pz)} ] (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 separati...

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Bibliographic Details
Published in:Chemistry : a European journal 2018-12, Vol.24 (70), p.18743-18748
Main Authors: Arnal, Lorenzo, Fuertes, Sara, Martín, Antonio, Baya, Miguel, Sicilia, Violeta
Format: Article
Language:English
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Summary:The X-ray study on a single crystal of the butterfly-like complex [{Pt(C^C*)(μ-pz)} ] (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 CHI in the air and the sunlight, complex [{Pt(C^C*)(μ-pz)I)} ] (2) (d =2.6079(2) Å) was obtained as the major product, while [IPt(C^C*)(μ-pz) Pt(C^C*)CHI ] (3) (d =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 Pt (II,II) "butterfly" by CHI to give metal-metal bonded Pt (III,III) compounds is described now for the first time.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201804013