Display options
Cite
Li J, Pinkerton AA, Finnen DC, et al. Multifunctional Ligands. Phosphinimine-Substituted Cyanofluoroaromatics Including X-ray Molecular Structures of Three Representative Ligands 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3))(2), 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2) and 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me). Formation of Rhodium(I) Complexes. Inorg Chem. 1996;35(19):5684-5692doi: 10.1021/ic951463m.
Li, J., Pinkerton, A. A., Finnen, D. C., Kummer, M., Martin, A., Wiesemann, F., & Cavell, R. G. (1996). Multifunctional Ligands. Phosphinimine-Substituted Cyanofluoroaromatics Including X-ray Molecular Structures of Three Representative Ligands 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3))(2), 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2) and 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me). Formation of Rhodium(I) Complexes. Inorganic chemistry, 35(19), 5684-5692. https://doi.org/10.1021/ic951463m
Li, Jin, et al. "Multifunctional Ligands. Phosphinimine-Substituted Cyanofluoroaromatics Including X-ray Molecular Structures of Three Representative Ligands 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3))(2), 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2) and 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me). Formation of Rhodium(I) Complexes." Inorganic chemistry vol. 35,19 (1996): 5684-5692. doi: https://doi.org/10.1021/ic951463m
Li J, Pinkerton AA, Finnen DC, Kummer M, Martin A, Wiesemann F, Cavell RG. Multifunctional Ligands. Phosphinimine-Substituted Cyanofluoroaromatics Including X-ray Molecular Structures of Three Representative Ligands 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3))(2), 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2) and 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me). Formation of Rhodium(I) Complexes. Inorg Chem. 1996 Sep 11;35(19):5684-5692. doi: 10.1021/ic951463m. PMID: 11666762.
Copy Download .nbib Format: NLM
Share it on

Inorg Chem. 1996 Sep 11;35(19):5684-5692. doi: 10.1021/ic951463m.

Multifunctional Ligands. Phosphinimine-Substituted Cyanofluoroaromatics Including X-ray Molecular Structures of Three Representative Ligands 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3))(2), 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2) and 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me). Formation of Rhodium(I) Complexes.

Inorganic chemistry

Jin Li, A. Alan Pinkerton, Daniel C. Finnen, Mattias Kummer, Anthony Martin, Frank Wiesemann, Ronald G. Cavell

Affiliations

  1. Departments of Chemistry, University of Alberta, Edmonton, AB, Canada T6G 2G2, and University of Toledo, Toledo, Ohio 43606-3390.

PMID: 11666762 DOI: 10.1021/ic951463m

Abstract

Reaction of 1,3-dicyanotetrafluorobenzene with 2 equiv of (trimethylsilyl)iminophosphoranes gave the disubstituted derivatives 4,6-(CN)(2)C(6)F(2)-1,3-AB: 1, A = B = (N=PPh(3)); 2, A = B = (N=PPh(2)Me); and 3, A = (N=PPh(3)), B = (N=PPh(2)Me). Monosubstituted compounds of the type 2,4-(CN)(2)C(6)F(3)-1-A; notably 4, A = (N=PPh(3)), and 5, A = (N=PPh(2)Me), were readily obtained by reaction of 1 molar equiv of the silylated iminophosphorane with the cyanofluoro aromatic. Substitution of the fluorine para to the CN group(s) occurs in all cases. Reactions of 1,2- and 1,4-dicyanotetrafluorobenzene with (trimethylsilyl)iminophosphoranes gave only monosubstituted derivatives 3,4-(CN)(2)C(6)F(3)-1-A (6, A = (N=PPh(3)), and 7, A = (N=PPh(2)Me)) and 2,5-(CN)(2)C(6)F(3)-1-A (8, A = (N=PPh(3)), and 9, A = (N=PPh(2)Me)), respectively, as the result of electronic deactivation of the second substitutional point. 1, 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(3)), 2, 4,6-(CN)(2)C(6)F(2)-1,3-(N=PPh(2)Me)(2), and 3, 4,6-(CN)(2)C(6)F(2)-1-(N=PPh(3))-3-(N=PPh(2)Me) have been structurally characterized. For 1 (at 21 degrees C), monoclinic, C2/(c) (No. 15), a = 15.289(2) Å, b = 10.196(1) Å, c = 23.491(6) Å, beta = 91.63(2) degrees, V = 3660(2) Å(3), and Z = 4. The P=N bond length is 1.579(2) Å and the P(V)-N-C(phenyl) angle is 134.0(2) degrees. For 2, (at 21 degrees C) monoclinic, C2/(c) (No. 15), a = 18.694(2) Å, b = 8.576(1) Å, c = 40.084(4) Å, beta = 94.00(1) degrees, V = 6411(2) Å(3), and Z = 8. The P(1)=N(1) bond length is 1.570(4) Å, the P(2)=N(2) bond length is 1.589(3) Å, the P(1)-N(1)-C(14) angle is 131.6(3) degrees, and the P(2)-N(2)-C(16) angle is 131.3(3) degrees. For 3, (at -80 degrees C) monoclinic, P2(1)/c (No. 14), a = 9.210(1) Å, b = 18.113(2) Å, c = 20.015(2) Å, beta = 100.07(1) degrees, V = 3287(2) Å(3), and Z = 4. The P(1)=N(1) bond length (PPh(3) group) is 1.567(4) Å, the P(2)=N(2) bond length (PPh(2)Me group) is 1.581(5) Å, the P(1)-N(1)-C(1) angle is 140.4(4) degrees, and the P(2)-N(2)-C(3) angle is 129.4(4) degrees. These new multifunctional chelating ligands readily react with [Rh(cod)Cl](2) and AgClO(4) to give cationic Rh(I) complexes in which the imine and/or the nitrile groups are coordinated to the Rh center.

Publication Types