Chemie polyfunktioneller Liganden, 57 [1] Über Iridium(I)- und Platin(II)-Komplexe des Bis(diphenylphosphino)amins und die oxidative Addition kleiner Moleküle an Di[bis(diphenylphosphino)amin-P.P']iricUum(I)-chlorid / Chemistry of Polyfunctional Ligands, 57[1] About Iridium(I) and Platinum(II) Complexes of Bis(diphenylphosphino)amine and the Oxidative Addition of Small Molecules to Di[bis(diphenylphosphino)amine]iridium(I)-chloride

Abstract

<jats:p>R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub> (1) (R = C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>) reacts with [(μ-Cl)Ir(C<jats:sub>8</jats:sub>H<jats:sub>12</jats:sub>)]<jats:sub>2</jats:sub> in a molar ratio of 4:1, to give the square planar, ionic complex [Ir(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (2a). By reaction of 2a with NaBR<jats:sub>4</jats:sub>, [Ir(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]BR<jats:sub>4</jats:sub> (2b) is obtained. Treatment of 2 a with CO gives [Ir(CO)(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (3a). The complex 3a is also formed by the reaction of 1 with Ir(CO)(PR<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>Cl (R = C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>) and Ir(CO)<jats:sub>2</jats:sub>(p-H<jats:sub>2</jats:sub>N-C<jats:sub>6</jats:sub>H<jats:sub>4</jats:sub>-CH<jats:sub>3</jats:sub>)Cl. 3a undergoes metathesis with NH<jats:sub>4</jats:sub>PF<jats:sub>6</jats:sub> to yield [Ir(CO)(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]PF<jats:sub>6</jats:sub> (3b). The N-deuterated derivative [Ir(CO)(R<jats:sub>2</jats:sub>PNDPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (4) is made by H/D exchange from 3a with CH<jats:sub>3</jats:sub>OD. Oxidative additions of O<jats:sub>2</jats:sub> , CS<jats:sub>2</jats:sub>, I<jats:sub>2</jats:sub> and (SCN)<jats:sub>2</jats:sub> to 2a yield [Ir(O<jats:sub>2</jats:sub>)(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (5), [Ir(μ<jats:sup>2</jats:sup>-CS<jats:sub>2</jats:sub>)(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (6), [Ir(I)<jats:sub>2</jats:sub>(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (7) and [Ir(SCN)<jats:sub>2</jats:sub>(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl (8). Additionally K<jats:sub>2</jats:sub>[PtCl<jats:sub>4</jats:sub>] and 1 reacts to [Pt(R<jats:sub>2</jats:sub>PNHPR<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>]Cl<jats:sub>2</jats:sub> (9). The new compounds are characterised, as far as possible, by their IR, FIR, Raman and <jats:sup>31</jats:sup>P NMR spectra.</jats:p>