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Böttcher, Hans‐Christian; Mayer, Peter und Karaghiosoff, Konstantin (2020): Spontaneous Reductive Elimination at Iridium(III) Induced by the Strong π‐Acceptor Ligand Trifluorophosphane. In: ZAAC, Bd. 646, Nr. 13: S. 558-560 [PDF, 231kB]

Abstract

The reaction of the cyclometalated five‐coordinate 16 VE iridium(III) compound [IrCl(H)(P(tBu)2C6H4‐κ2P,C)(P(tBu)2Ph)] (1) with the strong π‐acceptor ligand trifluorophosphane resulted quickly in the quantitative formation of the new iridium(I) complex trans‐[IrCl(PF3)(P(tBu)2Ph)2] (2). This unexpected spontaneous reductive elimination was already observed in reactions of 1 with the very strong π‐acceptor ligands CO and NO+. First indications during reactions of 1 with lesser strong π‐acceptor ligands like alkyl or arylphosphanes did not show this inversion behavior of the cyclometalation. The title species 2 was characterized by spectroscopic methods and its molecular structure in the crystal was confirmed by X‐ray crystallography.

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