1H,1H,2H,2H-perfluoroalkyl-functionalization of Ni(II), Pd(II), and Pt(II) mono- and diphosphine complexes: minimizing the electronic consequences for the metal center.
A series of fluorous derivatives of group 10 complexes MCl(2)(dppe) and [M(dppe)(2)](BF(4))(2) (M = Ni, Pd or Pt; dppe = 1,2-bis(diphenylphosphino)ethane) and cis-PtCl(2)(PPh(3))(2) was synthesized. The influence of para-(1H,1H,2H,2H-perfluoroalkyl)dimethylsilyl-functionalization of the phosphine phenyl groups of these complexes, as studied by NMR spectroscopy, cyclovoltammetry (CV), XPS analyses, as well as DFT calculations, points to a weak steric and no significant inductive electronic effect. The steric effect is most pronounced for M = Ni and leads in the case of NiCl(2)(1c) (3c) and [Ni(1c)(2)](BF(4))(2) (7c) (1c = [CH(2)P[C(6)H(4)(SiMe(2)CH(2)CH(2)C(6)F(13))-4](2)](2)) to a tetrahedral distortion from the expected square planar geometry. The solubility behavior of NiCl(2)[CH(2)P[C(6)H(4)(SiMe(3-b)(CH(2)CH(2)C(x)F(2x+1)b)-4](2)](2) (3: b = 1-3; x = 6, 8) in THF, toluene, and c-C(6)F(11)CF(3) was found to follow the same trends as those observed for the free fluorous ligands 1. A similar correlation between the partition coefficient (P) of complexes 3 and free 1 was observed in fluorous biphasic solvent systems, with a maximum value obtained for 3f (b = 3, x = 6, P = 23 in favor of the fluorous phase).
de Wolf
Elwin
E
Department of Metal-Mediated Synthesis, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Mens
Ad J M
AJ
Gijzeman
Onno L J
OL
van Lenthe
Joop H
JH
Jenneskens
Leonardus W
LW
Deelman
Berth-Jan
BJ
van Koten
Gerard
G