Dinuclear Paddle-Wheel Copper(II) Carboxylates in the Catalytic Oxidation of Carboxylic Acids. Unusual Polymeric Chains Found in the Single-Crystal X-ray Structures of [Tetrakis(&mgr;-1-phenylcyclopropane-1-carboxylato-O,O')bis(ethanol-O)dicopper(II)] and catena-Poly[[bis(&mgr;-diphenylacetato-O:O')dicopper](&mgr;(3)-diphenylacetato-1-O:2-O':1'-O')(&mgr;(3)-diphenylacetato-1-O:2-O':2'-O')].
The X-ray structures and spectroscopic and magnetic properties of [tetrakis(&mgr;-1-phenylcyclopropane-1-carboxylato-O,O')bis(ethanol-O)dicopper(II)], 1, and catena-poly[[bis(&mgr;-diphenylacetato-O:O')dicopper](&mgr;(3)-diphenylacetato-1-O:2-O':1'-O')(&mgr;(3)-diphenylacetato-1-O:2-O':2'-O')], 2, two extended-chain copper(II) carboxylates with dinuclear paddle-wheel subunits, are reported. 1 crystallizes in the triclinic space group P&onemacr;, with a = 6.8873(3) Å, b = 11.7367(6) Å, c = 13.7899(7) Å, alpha = 107.076(4) degrees, beta = 93.545(4) degrees, gamma = 103.967(4) degrees, Z = 1. The Cu.Cu distance is 2.6009(4) Å, and the Cu.carboxylate O distances are in the range 1.937(2)-1.962(2) Å. The ethanol at the apex forms an unsymmetrical bifurcated H bond to two carboxylate oxygens of another dinuclear unit with O.O distances 2.980(3) and 3.108(3) Å, thereby extending the structure along the a-axis. The magnetic structure consists of isolated antiferromagnetically coupled dinuclear copper units, with a -2J value of 242 cm(-)(1), in concurrence with the EPR parameters, viz., g(x)() = 2.03(1), g(y)() = 2.07(1), g(z)() = 2.35(1), A( parallel) = 0.064(2) cm(-)(1), D = 0.316(15) cm(-)(1), E = 0.005(1) cm(-)(1). The -2J value is the smallest value measured for dinuclear copper carboxylates with oxygen-donor ligands at the axial position and no electron-withdrawing carboxylate R groups. 2 crystallizes in the monoclinic space group P2(1)/c, with a = 15.953(2) Å, b = 5.385(6) Å, c = 28.322(10) Å, beta = 120.22(3) degrees, Z = 2. The compound contains tetrakis(diphenylacetato)dicopper(II) units, forming a polymeric structure along the b-axis by axial coordination of a carboxylate oxygen to copper of a subsequent dinuclear unit, at 2.323(11) Å. The intradimer Cu.Cu distance is 2.594(4) Å; the interdimer Cu.Cu distance is 3.425(5) Å. The -2J value of 321 cm(-)(1) was interpreted as originated from isolated antiferromagnetically coupled dinuclear copper units. The EPR parameters are g(x)() = 2.07(1), g(y)() = 2.02(1), g(z)() = 2.33(1), D = 0.347(10) cm(-)(1), E = 0.0034(5) cm(-)(1). The dinuclear subunits are likely candidates for the catalytically active Cu species in copper(II)-catalyzed oxidation of carboxylic acids.
Agterberg
Frank P. W.
FP
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands, DSM Research, P.O. Box 18, 6160 MD, Geleen, The Netherlands, and Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Provó Kluit
Hajo A. J.
HA
Driessen
Willem L.
WL
Oevering
Henk
H
Buijs
Wim
W
Lakin
Miles T.
MT
Spek
Anthony L.
AL
Reedijk
Jan
J