RHODIUM(I) AND RHODIUM(III) COMPLEXES CONTAINING SCHIFF-BASE LIGANDS

The reaction of [RhCl(C2H4)2]2 with the thallium Schiff-base derivatives Tl(SalNR) (SalNR = N-p-tolylsalicylaldimine (R = p-tol), N-methylsalicylal-dimine (R = Me)) gives [Rh(SalNR)(C2H4)2]. Reaction with tertiary phosphines and arsines yields the complexes [Rh(Salz.dbnd;NR))C2H4)L] (L = P(C6H5)3, As(C6H5)3; R = Me, p-tol) and [Rh(SalNR)L2] (L = P(C6H5)3, P(C6H5)2CH3; R = Me) while with certain di(tertiary phosphines) and -arsines yields [Rh(SalNR)(L2)] (L2 = 1,2-bis(diphenylarsino)ethane, cis-1,2-bis(diphenylarsino)-ethylene, cis-1,2-bis(diphenylphosphino)ethylene, R = p-tol, Me). The complexes [Rh(SalNMe)(L)2] readily add methyl iodide to give [Rh(CH3)I(SalNMe)(L)2] (L = P(C6H5)3, P(C6H5)2CH3) while the former also reacts with chloroform to yield [RhCl2(Salz.dbnd;NMe)(P(C6H5)3)2]. Hexafluorobut-2yne adds to [Rh(SalNp-tol)((C6H5)2AsCH2CH2As(C6H5)2)] to give [Rh(C4F6)(SalNp-tol)((C6H5)2AsCH2CH2As(C6H5)2] in which the acetylene undergoes hindered rotation. The infrared and 1H NMR spectra of these complexes are discussed. Also reported are several attempts at preparing oxidative addition compounds and derivatives with other ligands. © 1979.