The Chemistry of Chromium Nitrile Complexes of 1,2-Bis(dimethylphosphino)ethane. X-Ray Crystal Strucutres of trans-IVCl(NEt)(dmpe)2>CF3SO3, trans-IV(N=CHMe)2(dmpe)2>2, and 0(H.NCMe)2(dmpe)2>2

DOI: 10.1039/DT9870002947

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2947 - 2954 (1987)

Update date:2022-09-26

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Authors:

Barron, Andrew R.

Salt, Julian E.

Wilkinson, Geoffrey

Motevalli, Majid

Hursthouse, Michael B.

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Article abstract of DOI:10.1039/DT9870002947

The interaction of CrCl2(dmpe)2 with NaBPh4 in MeCN at room temperature gives the partially substituted complex trans-IICl(NCMe)(dmpe)2>BPh4; when the reaction is carried out in refluxing MeCN the product is the previously characterised trans-II(NCMe)2(dmpe)2>2.The interaction of both nitrile complexes with methanol has been studied, and the X-ray structures of the products, trans-IVCl(NEt)(dmpe)2>CF3SO3 and trans-IV(N=CHMe)2(dmpe)2>2 respectively, have been determined.These are the first octahedral Cr^IV complexes.The interaction of trans-2 with H2 leads to a complex of stoicheiometry trans-2, whose structure has been confirmed by X-ray crystallography.Although hydrogens bound to acetonitrile were not detected either crystallographically or spectroscopically, the diamagnetism together with the values of the Cr-P distances eliminate the possibility of a Cr^II species and confirm the presence of Cr⁰.Two weakly acidic protons have been shown to be present chemically, and its is proposed that H⁺ is located on the electron density in the C<*>N bond.The chromium(III) complex trans,trans-<2(μ-O)>⁴⁺ is also described.