The reaction of the octachlorodirhenate(III) ion with methyl isocyanide giving the pentachloro(methylisocyano)rhenium(IV) ion

✍ Scribed by F.Albert Cotton; Phillip E. Fanwick; Patrick A. McArdle

• Book ID: 104138888
• Publisher: Elsevier Science
• Year: 1979
• Tongue: English
• Weight: 370 KB
• Volume: 35
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)93453-4

✦ Synopsis

Methyl isocyanide reacts rapidly with (NBu"&-RezQs in ethanol at 25 "C to give a green product, shown by X-my ctystallogmphic study to be (NBu"J [ReCYs(CNCHJ]. The [ReCls(CNCHJ-ion is essentially octahedml, with all cis Re-Cl distances in the range 2.316( 7) A to 2.336(7) A and the trans Re-Cl distance equal to 2.343(6), thus indicating little or no structural trans effect by the isocyanide ligand. The failure to find any simple substitution product, such as Rea&(C?NCH&, is consistent with other observations where strongly nacid ligands cause degradation of M-M multiple bonds, although we cannot entirely rule out the formation of a small amount of such a product, nor is the identit eJ of the oxidizing agent that converts'Rdn to R known. The compound crystallizes in space group

P2Jc with a= 11.255(3) A, b = 14.651(6) A, c = 16.274(6) A, /3 = 93.82(6)", V = 2677(3) 2, and Z = 4. The structure was refined to R1 = 0.065 and R, = 0.076 using 15.58 reflections with I > 3a(I) and corrected for absorption.