Oxidation of RhCl{P(C6H11)3}2 and an E.P.R. study of some rhodium(II) complexes

✍ Scribed by H.L.M. Van Gaal; J.M.J. Verlaak; T. Posno

• Publisher: Elsevier Science
• Year: 1977
• Tongue: English
• Weight: 837 KB
• Volume: 23
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)94740-6

✦ Synopsis

RhX(PCy,)2 (X = Cl, Br, I; Cy = cyclohexyl) can be oxidized with halogens CIZ, BrZ and I2 to paramagnetic complexes RhXY(PCy& (X = Cl, Y = Br, I; X = Y = Br). From RhX(PClyJ2 and HY the monohydrides RhHXY(PCy& (X = Cl, Y = Cl, Br, I; X = Y = Br) have been prepared. RhCl(PCy,), reacts with CH,I to form either Rh(Me)ClI(PQ,), or Rh&leIZ(PCy,)2, depending on the reaction conditions. The formation of RhH,Cl(PCy,), and RhH,-(BH4)(PoJ2 is also described. The E.P.R. spectra of RhXY(PQ& and of RhC12(P(o-Tol)3)2 (o-To1 = ortho-tolyl) show large g-anisotropies,

and

to 1.6. Two possibilities for the Kramers doublet of the ground state, a mixture of approximately 80% d,z, 20% d,, and 1% d,,, and a mixture of approximately 80% d,.,, 20% dZ2 and 1% dxy, fit the experimental g-values reasonably well.