Abstract
R2PNHPR2 (1) (R = C6H5) reacts with [(μ-Cl)Ir(C8H12)]2 in a molar ratio of 4:1, to give the square planar, ionic complex [Ir(R2PNHPR2)2]Cl (2a). By reaction of 2a with NaBR4, [Ir(R2PNHPR2)2]BR4 (2b) is obtained. Treatment of 2 a with CO gives [Ir(CO)(R2PNHPR2)2]Cl (3a). The complex 3a is also formed by the reaction of 1 with Ir(CO)(PR3)2Cl (R = C6H5) and Ir(CO)2(p-H2N-C6H4-CH3)Cl. 3a undergoes metathesis with NH4PF6 to yield [Ir(CO)(R2PNHPR2)2]PF6 (3b). The N-deuterated derivative [Ir(CO)(R2PNDPR2)2]Cl (4) is made by H/D exchange from 3a with CH3OD. Oxidative additions of O2 , CS2, I2 and (SCN)2 to 2a yield [Ir(O2)(R2PNHPR2)2]Cl (5), [Ir(μ2-CS2)(R2PNHPR2)2]Cl (6), [Ir(I)2(R2PNHPR2)2]Cl (7) and [Ir(SCN)2(R2PNHPR2)2]Cl (8). Additionally K2[PtCl4] and 1 reacts to [Pt(R2PNHPR2)2]Cl2 (9). The new compounds are characterised, as far as possible, by their IR, FIR, Raman and 31P NMR spectra.

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