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Boettcher, Hans-Christian; Kluefers, Peter; Mies, Thomas and Mayer, Peter (2018): Synthesis and Molecular Structure of trans-[RhCl2(tBu(2)PPh)(2)]: a Rare Example of a Mononuclear Rhodium(II) Complex. In: Zeitschrift für Anorganische und Allgemeine Chemie, Vol. 644, No. 23: pp. 1593-1597

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During the reaction of [{Rh(mu-Cl)(coe)(2)}(2)] (1) (coe = cis-cyclooctene) with the tertiary phosphane tBu(2)PPh in a nitrogen atmosphere the square planar rhodium(II) complex trans-[RhCl2(tBu(2)PPh)(2)] (2) was identified as a side product in moderate yield. 2 was synthesized in a defined manner in higher yields using a known procedure starting from [{Rh(mu-Cl)(coe)(2)}(2)], tBu(2)PPh (molar ratio Rh:P of 1:2), and N-chlorosuccinimide as the oxidizing agent in THF at room temperature. The molecular structure of 2 was determined by X-ray crystallography. Additionally, to further confirm the molecular structure of trans-[RhCl2(tBu(2)PPh)(2)], extensive DFT calculations were undertaken, which gave further evidence for its molecular structure. In contrast to the remarkable stability of 2 in the solid state, the investigation of solutions of this compound afforded hints at a dynamic equilibrium, which renders more difficult the collection of adequate NMR spectroscopic data for the title complex.

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