TY - JOUR
T1 - Rhodium and Palladium Complexes of a 3,5-Lutidine-Based Phosphine Ligand
AU - Weisman, Alexander
AU - Gozin, Michael
AU - Kraatz, Heinz Bernhard
AU - Milstein, David
PY - 1996
Y1 - 1996
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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U2 - 10.1021/ic951131h
DO - 10.1021/ic951131h
M3 - Article
AN - SCOPUS:0001752286
VL - 35
SP - 1792
EP - 1797
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 7
ER -