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American Chemical Society, Inorganic Chemistry, 7(35), p. 1792-1797, 1996

DOI: 10.1021/ic951131h

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Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand

Journal article published in 1996 by Alexander Weisman, Michael Gozin, Heinz-Bernhard Kraatz ORCID, David Milstein
This paper is available in a repository.
This paper is available in a repository.

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Abstract

The chelating bis(phosphine) 3,5-bis((diphenylphosphino)methyl)pyridine (dppLH, 9) was synthesized from 3,5-lutidine by radical chlorination, followed by reaction with LiPPh2. Compound 9 was used to prepare Rh and Pd complexes. The three complexes (dppL)RhL (L = PiPr3 (11), PPh3 (12), and CO (13)) are obtained from Rh2Cl2(COE)4 (COE = cyclooctene) and HRh(PPh3)4. Compound 9 reacts with (PhCN)2PdCl2 to form the Pd(II) complex (dppL)PdCl (14). All complexes are fully characterized. The X-ray crystal structure of 11 has been determined. It crystallizes in the triclinic space group P1̄ (No. 2) with a = 12.242(3) Å, b = 14.384(3) Å, c = 11.653(2) Å, α = 98.61(2)°, β = 96.88(2)°, γ = 106.38(2)°, V = 2023.3(8) Å3, Z = 2, R = 0.045, and Rw = 0.052. The Rh(I) center is in a square-planar coordination environment with the two phosphines of the dppL ligand framework being trans to each other. The pyridine nitrogen is unobstructed and available for binding to other metal centers. Compound 14 acts as a metalloligand toward Pd(II) centers to form the trinuclear complex {(dppL)PdCl}2PdCl2 (16). N-coordination of a metal moiety and of a Lewis acid influences the electronic properties on the Pd center.