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1 Supporting Information Characterization of Intermediates in the C F Activation of the Tetrafluorobenzenes Using a Reactive Ni(PEt 3 ) 2 Synthon: A Combined Computational and Experimental Investigation Samuel A. Johnson*, Natalia M. Mroz, Rene Valdizon, Scott Murray Department of Chemistry & Biochemistry, University of Windsor, Windsor, ON, Canada, N9B 3P4. To whom correspondence should be addressed. sjohnson@uwindsor.ca. Fax: (519) Contents: pages 1-6 Selected spectra of complexes pages 7-32 Optimized xyz coordinates and energies for DFT calculations pages Details of X-ray structure solution and disorder modelling for 6 and 12. 1
2 Figure 1. Typical experimental 298 K 31 P{ 1 H} K MHz NMR spectrum for 2. Spectrum is of crude reaction mixture prepared by heating a pentane solution of (PEt 3 ) 2 NiMe 2 saturated with isobutene at 60 C for 2 h Figure 2. Experimental 298 K 282 MHz 19 F{ 1 H} K NMR resonances for 3. 2
3 Figure 3. Experimental 298 K 19 F{ 1 H} K 282 MHz NMR resonances for Figure 4. Experimental 298 K 19 F{ 1 H} K 282 MHz NMR resonances for Figure 5. Experimental 273 K 19 F{ 1 H} K 282 MHz NMR resonances for 6. 3
4 Figure 6. Experimental 253 K 282 MHz 19 F{ 1 H} NMR resonances for 7. * doublet due to Figure 7. Experimental low-temperature limit (193 K) 19 F{ 1 H} K 282 MHz NMR resonances for 9. 4
5 Figure 8. Experimental 293 K 19 F{ 1 H} K 282 MHz NMR resonances for 10. 5
6 model expt model expt model expt model expt Figure 9. Experimental and modelled 293 K 282 MHz 19 F NMR resonances for 11. 6
7 DFT Calculations 3 Me Me Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Optimized Coordinates F C Ni F C C C C Ni F C F P P P P C H H H C H H H C H H H C H H H C H H
8 H C H H H C H H H C H H H C H H H C H H H C H H H C H H H H H Me Optimized Coordinates F F C Ni C C C C Ni H C F F P P P
9 P C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H H
10 4 Me Me -23 Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me -12 Optimized Coordinates F C F C C C C Ni F C F P P C H H H C H H H C H H H C H H H C H H H C H H H H
11 H Me -23 Optimized Coordinates F F C C C C C Ni H C F F P P C H H H C H H H C H H H C H H H C H H H C H H H H Zero-point correction
12 Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Optimized Coordinates Ni H P P C C C C C C F F F F C H H H C H H H C H H H C H H H C H H H C H H H H
13 6 Me Me Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Me Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Optimized Coordinates F F C Ni F C C C C Ni F C H P P P P C H H H C
14 H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H H Me Optimized Coordinates F C Ni F
15 C C C C Ni C F F P P P P C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H
16 H H C H H H C H H H H H Me Optimized Coordinates F F C Ni C C C C Ni F C F P P P P C H H H C H H H C H H H C H H H C H H H
17 C H H H C H H H C H H H C H H H C H H H C H H H C H H H H H Me Optimized Coordinates F F C Ni F C C C C Ni H C F P P P P C
18 H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H H
19 7 Me Me -23 Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Me -56 Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me -23 Optimized Coordinates F C C C C C Ni F C F F P P C H H H C H H H C H H
20 H C H H H C H H H C H H H H H Me -45 Optimized Coordinates F C F C C C C Ni H C F F P P C H H H C H H H C H H H C H H H C
21 H H H C H H H H Me -12 Optimized Coordinates F F C C C C C Ni F C F P P C H H H C H H H C H H H C H H H C H H H C H H H H H
22 7 Me -56 Optimized Coordinates F F F F C C C C C Ni C P P C H H H C H H H C H H H C H H H C H H H C H H H H H Me Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies
23 8 Me Optimized Coordinates Ni H P P C C C C C C F F F F C H H H C H H H C H H H C H H H C H H H C H H H H Me Me Me Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies
24 Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Optimized Coordinates F F C Ni C C C C Ni F C F H P P P P C H H H C H H H C H H H C H H H C H H H C H H H C H
25 H H C H H H C H H H C H H H C H H H C H H H H Me Optimized Coordinates F C Ni F C C C C Ni F C F H P P P P C H H H C H H H
26 C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H H Me Optimized Coordinates F F C Ni F C C
27 C C Ni H C F P P P P C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H C H H H
28 C H H H C H H H H Me Me Me -12 Zero-point correction Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me -34 Optimized Coordinates F C F C C C C Ni H C F F P P C H H H C H H H C H H H
29 C H H H C H H H C H H H H Me -45 Optimized Coordinates F F C F C C C C Ni H C F P P C H H H C H H H C H H H C H H H C H H H C
30 H H H H Me -12 Optimized Coordinates F C C C C C Ni F C F F P P C H H H C H H H C H H H C H H H C H H H C H H H H H Me Zero-point correction
31 Thermal correction to Energy Thermal correction to Enthalpy Thermal correction to Gibbs Free Energy Sum of electronic and zero-point Energies Sum of electronic and thermal Energies Sum of electronic and thermal Enthalpies Sum of electronic and thermal Free Energies Me Optimized Coordinates Ni H P P C C C C C C F F F F C H H H C H H H C H H H C H H H C H H H C H H H H
32 X-ray Crystallographic Structure of 6. The solid-state structure of 6 contained two molecules in the asymmetric unit. Both molecules displayed a disorder of the tetrafluoroarene moiety consistent with the fact that there are two orientations by which the 1,2,3,4-tetrafluorobenzene can bind to the pair of nickel moieties in these dinuclear compounds and still provide the same isomer. This disorder is not surprising considering the similar size of hydrogen and fluorine. The molecule containing Ni(1) and Ni(2) displayed only a partial disorder of the 1,2,3,4-tetrafluoroarene moiety, with refined 0.845(4) and 0.155(4) site occupancies of the two possible arrangements. The second molecule displayed equal contributions from both possible arrangements of the tetrafluoroarene ring. The model for the fluorine atom disorder is provided in Figure 10. Molecule 1 F(4) F(4) F(3) Ni(2) H(5) F(3) Ni(2) F(22) Ni(1) Ni(1) F(2) C(2) C(1) H(6) H(2) C(2) C(1) F(12) F(1) H(1) Occupancy = 0.845(4) Occupancy = 0.155(4) F(8) Molecule 2 F(8) F(7) Ni(4) H(35) F(7) Ni(4) F(62) Ni(3) Ni(3) F(6) C(32) C(31) H(36) H(2) C(32) C(31) F(52) F(5) H(1) Occupancy = 0.5 Occupancy = 0.5 Figure 10. Solid-state disorder model for the 1,2,3,4-tetrafluorobenzene moiety in
33 The PEt 3 group associated with P(5) also exhibited 2-fold disorder of the Et groups, which was fully modeled, and is likely associated with the disorder of the tetrafluoroarene ring. The refined occupancies of all the disordered atoms and the treatment of their thermal parameters as anisotopic (Uani) or isotropic (Uiso) are provided below: F1 Uani 0.845(4) F2 Uani 0.845(4) F12 Uiso 0.155(4) F22 Uiso 0.155(4) H1 Uiso 0.155(4) H2 Uiso 0.155(4) H5 Uiso 0.845(4) H6 Uiso 0.845(4) F5 Uani 0.5 F6 Uani 0.5 F52 Uani 0.5 F62 Uani 0.5 H32 Uiso 0.5 H35 Uiso 0.5 H36 Uiso 0.5 H31 Uiso 0.5 C37A Uiso 0.5 H37A Uiso 0.5 H37B Uiso 0.5 C38A Uiso 0.5 H38A Uiso 0.5 H38B Uiso 0.5 H38C Uiso 0.5 C39A Uiso 0.5 H39A Uiso 0.5 H39B Uiso 0.5 C40A Uiso 0.5 H40A Uiso 0.5 H40B Uiso 0.5 H40C Uiso 0.5 C41A Uiso 0.5 H41A Uiso 0.5 H41B Uiso 0.5 C42A Uiso 0.5 H42A Uiso 0.5 H42B Uiso 0.5 H42C Uiso 0.5 C37B Uiso 0.5 H37C Uiso 0.5 H37D Uiso 0.5 C38B Uiso 0.5 H38D Uiso 0.5 H38E Uiso 0.5 H38F Uiso 0.5 C39B Uiso 0.5 H39C Uiso 0.5 H39D Uiso 0.5 C40B Uiso 0.5 H40D Uiso 0.5 H40E Uiso 0.5 H40F Uiso 0.5 C41B Uiso 0.5 H41C Uiso 0.5 H41D Uiso 0.5 C42B Uiso 0.5 H42D Uiso 0.5 H42E Uiso 0.5 H42F Uiso 0.5 X-ray Crystallographic Structure of 12. The asymmetric unit of 12 contains two molecules. Three of the PEt 3 moieties associated with molecule 2, which contains Ni(3) and Ni(4), exhibited disorder. Of these three PEt 3 groups, the moiety associated with P(7) featured rotational disorder about the Ni-P bond, which results in two orientations of the ethyl groups. The PEt 3 groups associated with P(6A,6B) features two sets of ethyl substituents, but also two slightly separated sites for the phosphorus atoms. A similar disorder was observed for P(8A,8B). For these groups, only two carbons appeared coincident, and were thus treated as full 33
34 occupation sites. Thermal parameters for atoms in sites with less than full occupancy were treated isotropically. No restraints were used in the disorder model. The occupancies for the three two-fold disordered PEt 3 groups were refined separately; values near 0.5 were obtained for all three PEt 3 groups. There is also a disorder of the fluorine atom site occupation, which is expected considering the similar sizes of fluorine and hydrogen. The site occupancy on both molecules were found to be nearly identical, and so were refined using a single variable. The atoms F(5) and F(5B) were found to have refined occupancies of 0.578(3) and 0.422(3), respectively. Similar occupancies were observed for F(2B) and F(2). The hydrogen atoms associated with these disordered sites were also given the appropriate occupancies. The refined occupancies of all the disordered atoms are provided below: F (3) F2B 0.578(3) P6A 0.544(2) P6B 0.456(2) P8A (19) P8B (19) F (3) F5B 0.428(3) H (3) H (3) C43A 0.544(2) H43A 0.544(2) H43B 0.544(2) C44A 0.544(2) H44A 0.544(2) H44B 0.544(2) H44C 0.544(2) C45A 0.544(2) H45A 0.544(2) H45B 0.544(2) C46A 0.544(2) H46A 0.544(2) H46B 0.544(2) H46C 0.544(2) C47A 0.544(2) H47A 0.544(2) H47B 0.544(2) C48A 0.544(2) H48A 0.544(2) H48B 0.544(2) H48C 0.544(2) C43B 0.456(2) H43C 0.456(2) H43D 0.456(2) C44B 0.456(2) H44D 0.456(2) H44E 0.456(2) H44F 0.456(2) C45B 0.456(2) H45C 0.456(2) H45D 0.456(2) C46B 0.456(2) H46D 0.456(2) H46E 0.456(2) H46F 0.456(2) C47B 0.456(2) H47C 0.456(2) H47D 0.456(2) C48B 0.456(2) H48D 0.456(2) H48E 0.456(2) H48F 0.456(2) C57A (19) H57A (19) H57B (19) C58A (19) H58A (19) H58B (19) H58C (19) C59A (19) H59A (19) H59B (19) C60A (19) H60A (19) H60B (19) H60C (19) C57B (19) H57C (19) H57D (19) C58B (19) H58D (19) H58E (19) H58F (19) C59B (19) H59C (19) H59D (19) C60B (19) H60D (19) H60E (19) H60F (19) C49A 0.488(3) 34
35 H49A 0.488(3) H49B 0.488(3) C50A 0.488(3) H50A 0.488(3) H50B 0.488(3) H50C 0.488(3) C51A 0.488(3) H51A 0.488(3) H51B 0.488(3) C52A 0.488(3) H52A 0.488(3) H52B 0.488(3) H52C 0.488(3) C53A 0.488(3) H53A 0.488(3) H53B 0.488(3) C54A 0.488(3) H54A 0.488(3) H54B 0.488(3) H54C 0.488(3) C49B 0.512(3) H49C 0.512(3) H49D 0.512(3) C50B 0.512(3) H50D 0.512(3) H50E 0.512(3) H50F 0.512(3) C51B 0.512(3) H51C 0.512(3) H51D 0.512(3) C52B 0.512(3) H52D 0.512(3) H52E 0.512(3) H52F 0.512(3) C53B 0.512(3) H53C 0.512(3) H53D 0.512(3) C54B 0.512(3) H54D 0.512(3) H54E 0.512(3) H54F 0.512(3) 35
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