3.7. Procedimientos de evaluación del aprendizaje de los alumnos
3.7.7. Tabla resumen de los procedimientos de evaluación del aprendizaje de los alumnos
The 1H pulsed field gradient spin-echo measurements were carried out without spinning and with a steady airflow of 670 l/h to prevent convection currents from the heating coil at 295 K (±0.1 K). The samples were dissolved in 0.7mL of CD2Cl2, with a concentration of 20 mM.
All the PGSE diffusion measurements were performed using the stimulated echo pulse sequence dstebpgp3s on a 400 MHz Bruker Avance spectrometer equipped with a TBI 1H/31P/BB HR probe. The pulse sequence was convection compensated and used bipolar pulses. A quadrangular gradient
120 pulse was used with a duration δ of 1.25 µs, and its strength varied automatically in the course of the experiments. The gradient system was calibrated using doped water as described in the Bruker diffusion user manuel. The data obtained were used to calculate the D values of the samples, according to the literature. In the 1H-PGSE experiments, the diffusion delay, Δ, was set to 100 µs, respectively. The number of scans was 8 per increment with a recovery delay of 2s. Typical experimental times were 30 minutes. All the spectra were acquired using 32 K points and processed with a line broadening of 1 Hz (1H).
Echo intensities and integrals were fit by non-linear regression to using the T1 processing package in TopSpin, to obtain the observed diffusion coefficients. Normally, 15-20 points were used for regression analysis, and all of the data leading to the reported D-values afforded lines whose correlation coefficients were >0.999. The gradient strength was incremented in 3-4% steps from 1 to 99%. The hydrodynamic radii, RH, were estimated using the Stokes-
Einstein equation, D = (kT)/(6πηrH), where η is the solution viscosity and rH
equals the hydrodynamic radius of the diffusing particles assuming a spherical shape.
The uncertainty of measurements can be judged from the reproducibility of the diffusion coefficient of dichloromethane, giving an uncertainty of ±9% for the diffusion coefficients.
121 3.4.3 Computational details
Methodology for structure optimisation utilising NOE
Initial structures were generated by use of a conformation distribution search carried out in Spartan ’08 using molecular mechanics and a MMFF94 force field with default parameters.25 The most popular structures which satisfied the key NOE signals previously identified were optimised using PC GAMESS.26 Structure optimisations were carried out at density functional theory (DFT) level in the gas phase using the B3LYP functional.27-30 For all the optimisations the 6-31G** basis set was used for all atoms except Ir.13 Relativistic effects for Ir were addressed by using LANL2DZ effective core potential (ECP) together with the LANL2DZ basis set.13
Due to the need to model the full complexity of the system while taking into consideration of the length of time this would require using a DFT level of theory, subsequent calculations were carried out in Gaussian09 at a semi- empirical level of theory using the PM6 Hamiltonian.14,15 A further optimisation followed by vibrational frequency calculations were carried out to confirm the nature of the stationary point on the potential energy surface. It was necessary to insert a dummy atom placed into the middle of the Cp* ring so that the coordination remained η5. The Ir to dummy atom distance was constrained to a value of 1.83 Å based on the crystal structure of C. Energy minima were confirmed with no imaginary frequencies less than -50 cm-1. All calculations were performed on the University of Liverpool linux clusters, and graphical representations were generated using chemcraft31 and CYLview.,32
122 3.5 Analytical data
All NMR data can be found attached in the supporting electronic information. All XYZ coordinates can also be found attached in the supporting elctronic information.
3.6 References
(1) Knowles, R. R.; Jacobsen, E. N. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 20678.
(2) Shao, Z.; Zhang, H. Chem. Soc. Rev.2009, 38, 2745. (3) Zhong, C.; Shi, X. Eur. J. Org. Chem.2010, 2999.
(4) Rueping, M.; Koenigs, R. M.; Atodiresei, I. Chem.-Eur. J. 2010, 16, 9350.
(5) Allen, A. E.; MacMillan, D. W. C. Chem. Sci.2012, 3, 633.
(6) Stegbauer, L.; Sladojevich, F.; Dixon, D. J. Chem. Sci.2012, 3, 942. (7) Yu, Z.; Jin, W.; Jiang, Q. Angew. Chem., Int. Ed.2012, 51, 6060. (8) Keeler, J. Understanding NMR spectroscopy; Wiley: Chichester,
England ; Hoboken, NJ, 2005.
(9) Orglmeister, E.; Burgi, T.; Mallat, T.; Baiker, A. J. Catal. 2005, 232, 137.
(10) Jiang, Q. Z.; Ruegger, H.; Venanzi, L. M. J. Organomet. Chem. 1995, 488, 233.
(11) Holyoak, T.; Nowak, T. Biochemistry2001, 40, 11037. (12) Turner, D. L. J. Magn. Reson., Ser B1995, 108, 137. (13) https://bse.pnl.gov/bse/portal.
123 (14) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Wallingford CT, 2009.
(15) Stewart, J. J. P. J. Mol. Model.2007, 13, 1173.
(16) Stejskal, E. O.; Tanner, J. E. J. Chem. Phys.1965, 42, 288.
(17) Pregosin, P. S.; Kumar, P. G.; Fernandez, I. Chem. Rev. 2005, 105, 2977.
(18) Cohen, Y.; Avram, L.; Frish, L. Angew. Chem., Int. Ed.2005, 44, 520. (19) Kumar, P. G. A.; Pregosin, P. S.; Goicoechea, J. M.; Whittlesey, M. K.
Organometallics2003, 22, 2956.
124 (21) Dydio, P.; Rubay, C.; Gadzikwa, T.; Lutz, M.; Reek, J. N. H. J. Am.
Chem. Soc.2011, 133, 17176.
(22) Ciardi, M.; Tancini, F.; Gil-Ramirez, G.; Escudero-Adan, E. C.; Massera, C.; Dalcanale, E.; Ballester, P. J. Am. Chem. Soc. 2012, 134, 13121.
(23) Nishio, M. Tetrahedron2005, 61, 6923.
(24) Storer, R. I.; Carrera, D. E.; Ni, Y.; MacMillan, D. W. J. Am. Chem. Soc.2006, 128, 84.
(25) http://wavefun.com/products/spartan.html.
(26) http://classic.chem.msu.su/gran/gamess/index.html A. A. Granovsky Firefly v7.1.G
(27) Becke, A. D. J. Chem. Phys.1993, 98, 5648.
(28) Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B1988, 37, 785. (29) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
(30) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys.
Chem.1994, 98, 11623.
(31) http://www.chemcraftprog.com.
125