Rhodium(I) and iridium(I) complexes of 2,2′-dipyridylamine and its deprotonated form

Abstract

The syntheses and properties of cationic and neutral rhodium(I) and iridium(I) complexes with the 2,2′-dipyridylamine ligand (Hdipy) and its deprotonated form (dipy) are reported. Representative general formulae are: [M(L 2)(Hdipy)]ClO 4 (M Rh, Ir; L 2 = diolefin, L  CO), [M(CO) 2(Hdipy)]- [MCl 2(CO) 2], [MCl(diolefin)(Hdipy)] and [M(dipy)- (diolefin)]. The latter complex still has an amide nitrogen available for coordination and is used for the syntheses of the binuclear complexes [(diolefin)- Rh(μ-dipy)Rh(CO)(PPh 3) 2]ClO 4 and [Rh 2(μ-dipy)- Cl(diolefin) 2]. The crystal and molecular structure of the complex [Rh(dipy)(nbd)] (nbd = 2,5-norbornadiene) has been determined by single-crystal X-ray methods. Crystals are triclinic, space group P 1 with cell constants a = 12.3651(4), b = 12.4386(3), c = 10.0809(3) Å, α = 103.209(2), β = 110.278(2), and γ = 88.125(2)°, and Z = 4. The final R and R w values were 0.033 and 0.039 for 4180 observations. The Rh atoms in the two independent molecules in the unit cell present similarly distorted square-planar geometries with both chelate ligands coordinated to each metal atom.