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Abstract
The synthesis of a new sexadentate ligand, P,P,P′,P′-tetrakis(2-diphenylarsinoethyl)α, α′-diphospha-p-xylene (TDADX) and the preparation of its iridium(I), rhodium(I) and ruthenium (II) complexes are described. When M=Ir and Rh, MCl(CO)(PPh3)2 reacts in benzene solution with the ligand TDADX to yield the complexes, [Ir(TDADX)] Cl and Rh2 Cl2 (TDADX). RuCl(CO)(PPh3)3 Cl reacts with this ligand to yield [RuCl(TDADX)]Cl. Complexes of P,P,P′,P′-tetrakis(2-diphenylphosphinoethyl-α,α-diphospha-p-xylene(TDDX) were also studied for comparison. Molecular hydrogen reacts with the complexes Ir2 Cl2 (TDDX), [Ir(TDADX)] Cl and [RuCl(TDADX)] Cl to form the corresponding hydrido complexes. Reaction of molecular oxygen with Rh2 Cl2 (TDADX) resulted in the formation of the dioxygen complex. Ir(I), Rh(I) and Ru(II) complexes of TDDX and TDADX react with carbonmonoxide to give mixed ligand carbonyl complexes. The complexes Ir2 Cl2 (TDDX), [Ir(TDADX)] Cl, and [RuCl(TDADX)] Cl react with nitric oxide to yield nitrosyl complexes. Infrared spectral data are provided for adducts formed with hydrogen, oxygen, carbon monoxide and nitric oxide.