Compounds containing weak, non-covalent interactions to the metal in the backbone of 1,1′-bis(phosphino)metallocene ligands

Add time:09/01/2019    Source:sciencedirect.com

The reactions of Na[BArF] (BArF = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) with a series of [Pd(dpEMc)Cl2] (dpEMc = 1,1′-bis(diphenylphosphino)ruthenocene (dppr), 1,1′-bis(diphenylphosphino)osmocene (dppo) or 1,1′-bis(diphenylarsino)ferrocene (dpaf)) compounds were examined. The reaction of Na[BArF] with [Pd(dppMc)Cl2] (dppMc = dppr or dppo) resulted in the formation of the corresponding chloride-bridged dimers, [Pd(dppMc)(μ-Cl)]22+, which were structurally characterized. However, these dimers appear to be unstable in CH2Cl2 and partially (Ru) or fully (Os) convert into the corresponding monomers, [Pd(dppMc)Cl]+, which are proposed to have a weak, non-covalent M–Pd (M = Ru or Os) interaction. Similar compounds, [Pd(dppo)PPh3]2+ and [Pt(dppMc)PPh3]2+ (M = Fe (1,1′-bis(diphenylphosphino)ferrocene (dppf)) or Os (dppo)), were also prepared and structurally characterized. These compound also exhibit weak, non-covalent M–Pd/Pt interactions. In addition, the electrochemical properties of these compounds were examined by cyclic voltammetry.

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