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

Alexander Weisman, Michael Gozin, Heinz Bernhard Kraatz, David Milstein

Research output: Contribution to journalArticle

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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.

Original languageEnglish
Pages (from-to)1792-1797
Number of pages6
JournalInorganic Chemistry
Volume35
Issue number7
Publication statusPublished - 1996

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phosphine
Rhodium
Palladium
rhodium
phosphines
palladium
Metals
Phosphines
Ligands
Lewis Acids
ligands
Chlorination
Carbon Monoxide
Chelation
Electronic properties
pyridines
Nitrogen
Crystal structure
X rays
chlorination

ASJC Scopus subject areas

  • Inorganic Chemistry

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Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand. / Weisman, Alexander; Gozin, Michael; Kraatz, Heinz Bernhard; Milstein, David.

In: Inorganic Chemistry, Vol. 35, No. 7, 1996, p. 1792-1797.

Research output: Contribution to journalArticle

Weisman, A, Gozin, M, Kraatz, HB & Milstein, D 1996, 'Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand', Inorganic Chemistry, vol. 35, no. 7, pp. 1792-1797.
Weisman, Alexander ; Gozin, Michael ; Kraatz, Heinz Bernhard ; Milstein, David. / Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand. In: Inorganic Chemistry. 1996 ; Vol. 35, No. 7. pp. 1792-1797.
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N2 - 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.

AB - 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.

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