SECCIÓN SÉPTIMA
DE LAS PROHIBICIONES A LOS TRABAJADORES Artículo
Single crystals of 1c were obtained from a CH2Cl2 solution layered with toluene. Crystals of 1g were obtained from a CH2Cl2/PhCH3 solution of the complex layered with a small amount of Br2 in CH2Cl2 solution. Diffraction data were collected either on a Bruker three-circle platform goniometer equipped with an Apex II CCD and an Oxford cryostream cooling device (100 K) with radiation from a graphite fine focus sealed tube Mo Kα
(0.71073 Å) source or on a vertically mounted Bruker D8 three-circle platform goniometer equipped with an Apex II CCD and an Oxford Diffraction Helijet cooling device (15 K) with synchrotron radiation (0.41328 Å) supplied to ChemMatCARS located at Advances Photon Source (APS), Argonne National Laboratory (ANL). Crystals were mounted on a glass fiber pin using Paratone N oil. Data was collected as a series of φ and/or ω scans. Data was integrated using SAINT and scaled with multi-scan absorption correction using SADABS.60 The structures were solved by intrinsic phasing using SHELXT (Apex2 program suite v2014.1)and refined against F2 on all data by full matrix least squares with SHELXL-97.61 All non-H atoms were refined anisotropically. H atoms were placed at idealized positions and refined using a riding model. Crystal data and refinement statistics are summarized in Table 3.5 and thermal ellipsoid plots are collected in Fig. 4. X-ray crystal structures of 1c,
1g, 3c and 3e are available from the Cambridge Crystal Structure Database (1040260, 1040259, 1401868, and 1401864, respectively).
111
NiCl3(dppb) (1c) NiBr3(dppb) (1g)
formula C30H24Cl3NiP2 C16.5H15Br1.5Cl3Ni0.5P CCDC # 1040260 1040259
fw, g/mol 611.49 499.83 temp, K 100 (2) 15 (2) cryst system Monoclinic Monoclinic space group P2(1) P2(1)/m color a, Å 9.7441 (9) 8.7809 (4) b, Å 14.730 (1) 21.401 (1) c, Å 10.2714 (9) 10.6362 (5) α, deg 90 90 β, deg 113.297 (2) 113.3720 (7) γ, deg 90 90 V, A3 1354.1 (2) 1834.8 (2) Z 2 4 R1a 0.0525 0.0187 wR2b 0.0861 0.0439 GOFc (F2) 0.983 1.039 Rint 0.0678 0.0210
a R1 = Σ||Fo – |Fc||/Σ|Fo|. bwR2 = (Σ(w(Fo2 – Fc2)2)/Σ(w(Fo2)2))1/2. c GOF = (Σw(Fo2 –
Fc2)2/(n – p))1/2 where n is the number of data and p is the number of parameters refined. Table 3.5. Crystal data and structure refinement for 1c and 1g.
112
Solution-Phase Calorimetry
Solution-phase calorimetry measurements were carried out using a Thermometric 2225 Precision Solution calorimeter. In the glove box, a CH2Cl2 solution of Ni(II) dichloride was prepared. This solution was transferred to the glass cell of the calorimeter, which was equipped with an ampule-breaking rod. A small glass ampule containing PhICl2 was added, sealed, and loaded into the calorimeter. Following temperature equilibration (achieved standard deviation of 2 μK after 2 h), the reaction was initiated by breaking the ampoule and rotating the calorimeter to ensure complete mixing. Electrical calibrations were run before and after breaking the ampoule. The enthalpy of chlorination of Ni(II) was
determined by subtracting half the enthalpy of chlorination of PhI from the experimentally measured reaction enthalpy. Measured data was corrected for the enthalpy of solution of the solid PhICl2, which was measured separately. Reported data is the average of three independent measurements.
Computational Details
All DFT calculations were performed using the Gaussian 09, Revision D.01 software suite.62 For all calculations, the B3LYP63–65 hybrid exchange-correlation functional was used in combination with a split basis set (TZVP66 for Ni, P, and Br; TZV67 for C and H). Starting geometries for gas-phase optimization were obtained from crystallographic coordinates; frequency calculations were carried out to ensure structures represented energetic minima. Geometries used for DFT calculations are available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.5b00568. Time-dependent DFT (TD-DFT) single point calculations were carried out on the gas-phase geometry optimized models using the same combination of functional and basis sets. Where used, solvation
113
effects were included using the polarized continuum model (PCM). Ground and excited state potential energy surfaces (PESs) for metal-apical halide bond loss were constructed using constrained geometry optimizations coupled to subsequent TD-DFT calculations. Charge decomposition analyses (CDA) were carried out using the AOMix program (revision 6.82).68 The degree of phosphine ligand donation was calculated using NiX3 and phosphine ligands as fragments; the degree of phosphine ligand donation was calculated as the
difference in total electron donation (sum of all occupied α and β molecular orbitals) from the phosphine ligand to NiX3 and back-donation between NiX3 and the phosphine ligand.
114
3.6 References
1. Rosenthal, J.; Nocera, D. G. Role of Proton-Coupled Electron Transfer in O–O Bond Activation. Acc. Chem. Res. 2007, 40 (7), 543–553.
2. Rosenthal, J.; Nocera, D. G. Oxygen Activation Chemistry of Pacman and Hangman Porphyrin Architectures Based on Xanthene and Dibenzofuran Spacers. In Progress in Inorganic Chemistry; Karlin, K. D., Ed.; John Wiley & Sons, Inc., 2007; pp 483–544. 3. Nicolet, Y.; Cavazza, C.; Fontecilla-Camps, J. C. Fe-Only Hydrogenases: Structure,
Function and Evolution. Journal of Inorganic Biochemistry2002, 91 (1), 1–8. 4. Nicolet, Y.; Lemon, B. J.; Fontecilla-Camps, J. C.; Peters, J. W. A Novel FeS Cluster in
Fe-Only Hydrogenases. Trends in Biochemical Sciences2000, 25 (3), 138–143. 5. Peters, J. W. Structure and Mechanism of Iron-Only Hydrogenases. Current Opinion
in Structural Biology1999, 9 (6), 670–676.
6. DuBois, M. R.; DuBois, D. L. The Roles of the First and Second Coordination Spheres in the Design of Molecular Catalysts for H2 Production and Oxidation. Chem. Soc. Rev.2008, 38 (1), 62–72.
7. Rakowski Dubois, M.; Dubois, D. L. Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation. Acc. Chem. Res.2009, 42 (12), 1974– 1982.
8. Bediako, D. K.; Solis, B. H.; Dogutan, D. K.; Roubelakis, M. M.; Maher, A. G.; Lee, C. H.; Chambers, M. B.; Hammes-Schiffer, S.; Nocera, D. G. Role of Pendant Proton Relays and Proton-Coupled Electron Transfer on the Hydrogen Evolution Reaction by Nickel Hangman Porphyrins. PNAS2014, 111 (42), 15001–15006.
9. McGuire, R. Jr.; Dogutan, D. K.; Teets, T. S.; Suntivich, J.; Shao-Horn, Y.; Nocera, D. G. Oxygen Reduction Reactivity of cobalt(II) Hangman Porphyrins. Chem. Sci.2010, 1
(3), 411–414.
10. Dogutan, D. K.; McGuire, R. Jr.; Nocera, D. G. Electocatalytic Water Oxidation by
Cobalt(III) Hangman β-Octafluoro Corroles. J. Am. Chem. Soc.2011, 133 (24), 9178–
9180.
11. Lee, C. H.; Dogutan, D. K.; Nocera, D. G. Hydrogen Generation by Hangman Metalloporphyrins. J. Am. Chem. Soc.2011, 133 (23), 8775–8777.
12. Borovik, A. S. Bioinspired Hydrogen Bond Motifs in Ligand Design: The Role of Noncovalent Interactions in Metal Ion Mediated Activation of Dioxygen. Acc. Chem. Res.2005, 38 (1), 54–61.
115
13. Park, Y. J.; Matson, E. M.; Nilges, M. J.; Fout, A. R. Exploring Mn–O Bonding in the Context of an Electronically Flexible Secondary Coordination Sphere: Synthesis of a Mn(III)–oxo. Chem. Commun.2015, 51 (25), 5310–5313.
14. Esswein, A. J.; Nocera, D. G. Hydrogen Production by Molecular Photocatalysis. Chem. Rev.2007, 107 (10), 4022–4047.
15. Nocera, D. G. Chemistry of Personalized Solar Energy. Inorg. Chem.2009, 48 (21), 10001–10017.
16. Teets, T. S.; Nocera, D. G. Photocatalytic Hydrogen Production. Chem. Commun.2011,
47 (33), 9268–9274.
17. Cook, T. R.; Surendranath, Y.; Nocera, D. G. Chlorine Photoelimination from a
Diplatinum Core: Circumventing the Back Reaction. J. Am. Chem. Soc.2009, 131 (1), 28–29.
18. Lin, T.-P.; Gabbaï, F. P. Two-Electron Redox Chemistry at the Dinuclear Core of a TePt Platform: Chlorine Photoreductive Elimination and Isolation of a TeVPtI Complex. J. Am. Chem. Soc.2012, 134 (29), 12230–12238.
19. Yang, H.; Gabbaï, F. P. Solution and Solid-State Photoreductive Elimination of Chlorine by Irradiation of a [PtSb]VII Complex. J. Am. Chem. Soc.2014, 136 (31), 10866–10869.
20. Raphael Karikachery, A.; Lee, H. B.; Masjedi, M.; Ross, A.; Moody, M. A.; Cai, X.; Chui, M.; Hoff, C. D.; Sharp, P. R. High Quantum Yield Molecular Bromine Photoelimination from Mononuclear Platinum(IV) Complexes. Inorg. Chem.2013, 52 (7), 4113–4119. 21. Perera, T. A.; Masjedi, M.; Sharp, P. R. Photoreduction of Pt(IV) Chloro Complexes:
Substrate Chlorination by a Triplet Excited State. Inorg. Chem.2014, 53 (14), 7608– 7621.
22. Teets, T. S.; Nocera, D. G. Halogen Photoreductive Elimination from Gold(III) Centers. J. Am. Chem. Soc.2009, 131 (21), 7411–7420.
23. Powers, D. C.; Chambers, M. B.; Teets, T. S.; Elgrishi, N.; Anderson, B. L.; Nocera, D. G. Halogen Photoelimination from Dirhodium Phosphazane Complexes via Chloride- Bridged Intermediates. Chem. Sci.2013, 4 (7), 2880–2885.
24. Cook, T. R.; Esswein, A. J.; Nocera, D. G. Metal−Halide Bond Photoactivation from a
PtIII−AuII Complex. J. Am. Chem. Soc.2007, 129 (33), 10094–10095.
25. Cook, T. R.; McCarthy, B. D.; Lutterman, D. A.; Nocera, D. G. Halogen Oxidation and Halogen Photoelimination Chemistry of a Platinum–Rhodium Heterobimetallic Core.
116
26. Teets, T. S.; Lutterman, D. A.; Nocera, D. G. Halogen Photoreductive Elimination from
Metal−Metal Bonded Iridium(II)−Gold(II) Heterobimetallic Complexes. Inorg. Chem.
2010, 49 (6), 3035–3043.
27. Creutz, C.; Chou, M.; Netzel, T. L.; Okumura, M.; Sutin, N. Lifetimes, Spectra, and Quenching of the Excited States of Polypyridine Complexes of iron(II),
ruthenium(II), and osmium(II). J. Am. Chem. Soc.1980, 102 (4), 1309–1319. 28. McCusker, J. K. Femtosecond Absorption Spectroscopy of Transition Metal Charge-
Transfer Complexes. Acc. Chem. Res.2003, 36 (12), 876–887.
29. Juban, E. A.; Smeigh, A. L.; Monat, J. E.; McCusker, J. K. Ultrafast Dynamics of Ligand- Field Excited States. Coordination Chemistry Reviews2006, 250 (13–14), 1783– 1791.
30. Bruin, B. D.; Hetterscheid, D. G. H.; Koekkoek, A. J. J.; Grützmacher, H. In Progress in Inorganic Chemistry; Karlin, K. D., Ed.; J. Wiley and Sons: New York, 2007; Vol. 55, p 247.
31. Bühler, R. E.; Ebert, M. Transient Charge-Transfer Complexes with Chlorine Atoms
by Pulse Radiolysis of Carbon Tetrachloride Solutions. Nature1967, 214 (5094), 1220–1221.
32. Strong, R. L.; Rand, S. J.; Britt, J. A. Charge-Transfer Spectra of Iodine Atom-Aromatic
Hydrocarbon Complexes1. J. Am. Chem. Soc.1960, 82 (19), 5053–5057. 33. Bossy, J. M.; Buehler, R. E.; Ebert, M. Pulse Radiolysis of Organic Halogen
Compounds. II. Transient Bromine-Atom Charge-Transfer Complexes Observed by Pulse Radiolysis. J. Am. Chem. Soc.1970, 92 (4), 1099–1101.
34. Förgeteg, S.; Bérces, T. Laser Flash Photolysis Study of Chlorine Atom/simple Arene
π-Complexes in Carbon Tetrachloride and Acetonitrile. Journal of Photochemistry
and Photobiology A: Chemistry1993, 73 (3), 187–195.
35. Sokolov, A. Y.; Schaefer III, H. F. Ground and excited state properties of photoactive platinum(iv) diazido complexes: Theoretical considerations. Dalton Trans. 2011, 40, 7571.
36. Tsao, M.-L.; Hadad, C. M.; Platz, M. S. Computational Study of the Halogen
Atom−Benzene Complexes. J. Am. Chem. Soc.2003, 125 (27), 8390–8399.
37. Dapprich, S.; Frenking, G. Investigation of Donor-Acceptor Interactions: A Charge
Decomposition Analysis Using Fragment Molecular Orbitals. J. Phys. Chem.1995, 99
117
38. Hendry, D. G.; Mill, T.; Piszkiewicz, L.; Howard, J. A.; Eigenmann, H. K. A Critical Review of H‐Atom Transfer in the Liquid Phase: Chlorine Atom, Alkyl,
Trichloromethyl, Alkoxy, and Alkylperoxy Radicals. Journal of Physical and Chemical Reference Data1974, 3 (4), 937–978.
39. Olbregts, J.; Brasseur, G.; Arijs, E. Reaction of Acetonitrile and Chlorine Atoms. Journal of Photochemistry1984, 24 (4), 315–322.
40. Raner, K. D.; Lusztyk, J.; Ingold, K. U. Ultraviolet/visible Spectra of Halogen
Molecule/arene and Halogen Atom/arene .pi.-Molecular Complexes. J. Phys. Chem. 1989, 93 (2), 564–570.
41. Alfassi, Z. B.; Huie, R. E.; Mittal, J. P.; Neta, P.; Shoute, L. C. T. Charge-Transfer
Complexes of Bromine Atoms with Haloalkanes and Alkanes. J. Phys. Chem.1993, 97
(36), 9120–9123
42. Rosker, M. J.; Dantus, M.; Zewail, A. H. Femtosecond Real‐time Probing of Reactions. I. The Technique. The Journal of Chemical Physics1988, 89 (10), 6113–6127.
43. Roberts, G.; Zewail, A. H. Femtosecond Real-Time Probing of Reactions. 7. A Quantum- and Classical-Mechanical Study of the Cyanogen Iodide Dissociation Experiment. J. Phys. Chem.1991, 95 (21), 7973–7993.
44. Della Ciana, L.; Dressick, W. J.; Sandrini, D.; Maestri, M.; Ciano, M. Synthesis and Characterization of a New Family of Luminescent Cis-(4,4’-X2-5,5’-Y2-2,2’-
bipyridine)2Os(CO)Cl(PF6) Complexes (X = NEt2, OMe, Me, H, Cl, Y = H; X = H, Y = Me; X = Y = Me): Control of Excited-State Properties by Bipyridyl Substituents. Inorg. Chem.1990, 29 (15), 2792–2798.
45. Takizawa, S.; Shimada, K.; Sato, Y.; Murata, S. Controlling the Excited State and Photosensitizing Property of a 2-(2-Pyridyl)benzo[b]thiophene-Based Cationic Iridium Complex through Simple Chemical Modification. Inorg. Chem.2014, 53 (6), 2983–2995.
46. Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Safe and Convenient Procedure for Solvent Purification. Organometallics1996, 15 (5), 1518– 1520.
47. Zielinska, A.; Skulski, L. A Solvent-Free Synthesis of (dichloroiodo)arenes from Iodoarenes. Tetrahedron Letters2004, 45 (5), 1087–1089.
48. Fawcett, J.; Hope, E. G.; Stuart, A. M.; Sherrington, J. Coordination Chemistry of 1,2- Bis{di-(4-Methoxyphenyl)phosphino}ethane (L-L) to Nickel, Palladium and
Platinum: Single Crystal Structures of [MCl2(L-L)] (M = Ni, Pd). Inorganica Chimica Acta2006, 359 (11), 3535–3539.
118
49. Gray, L. R.; Higgins, S. J.; Levason, W.; Webster, M. Co-Ordination Chemistry of Higher Oxidation States. Part 8. Nickel(III) Complexes of Bi- and Multi-Dentate Phosphorus and Arsenic Ligands; Crystal and Molecular Structure of
[Ni(Ph2PCH2CH2PPh2)Br3]·C6H5Me. J. Chem. Soc., Dalton Trans.1984, No. 3, 459– 467.
50. Zarkesh, R. A.; Hopkins, M. D.; Jordan, R. F. Halogenolysis of a Nickelalactone
Complex Produces β-Halo-Anhydrides. Eur. J. Inorg. Chem.2014, 2014 (32), 5491–
5494.
51. Bomfim, J. A. S.; de Souza, F. P.; Filgueiras, C. A. L.; de Sousa, A. G.; Gambardella, M. T. P. Diphosphine Complexes of Nickel: Analogies in Molecular Structures and Variety in Crystalline Arrangement. Polyhedron2003, 22 (12), 1567–1573.
52. Smeets, B. J. J.; Meijer, R. H.; Meuldijk, J.; Vekemans, J. A. J. M.; Hulshof, L. A. Process Design and Scale-Up of the Synthesis of 2,2‘:5‘,2‘ ‘-Terthienyl. Org. Process Res. Dev. 2003, 7 (1), 10–16.
53. Carroll, M. E.; Barton, B. E.; Gray, D. L.; Mack, A. E.; Rauchfuss, T. B. Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties. Inorg. Chem.2011, 50 (19), 9554–9563.
54. Angulo, I. M.; Bouwman, E.; Lutz, M.; Mul, W. P.; Spek, A. L. Autoionization of
Homogeneous Nickel(II) Diphosphane Hydrogenation Catalysts. An NMR Study and Crystal Structures of [Ni(o-MeO-dppe)I2] and [Ni(o-MeO-dppe)2](PF6)2. Inorg. Chem.2001, 40 (9), 2073–2082.
55. Jarrett, P. S.; Sadler, P. J. Nickel(II) Bis(phosphine) Complexes. Inorg. Chem.1991, 30
(9), 2098–2104.
56. Bain, G. A.; Berry, J. F. Diamagnetic Corrections and Pascal’s Constants. J. Chem. Educ.
2008, 85 (4), 532.
57. Stoll, S.; Schweiger, A. EasySpin, a Comprehensive Software Package for Spectral Simulation and Analysis in EPR. Journal of Magnetic Resonance2006, 178 (1), 42– 55.
58. Montalti, M.; Credi, A.; Prodi, L.; Gandolfi, M. T. Handbook of Photochemistry, 3rd ed.; Taylor and Francis: Boca Raton, 2006.
59. Holder, P. G.; Pizano, A. A.; Anderson, B. L.; Stubbe, J.; Nocera, D. G. Deciphering Radical Transport in the Large Subunit of Class I Ribonucleotide Reductase. J. Am. Chem. Soc.2011, 134 (2), 1172–1180.
119
61. Sheldrick, G. M. Experimental phasing with SHELXC/D/E: combining chain tracing
with density modification. Acta Cryst. 2010, D66, 479.
62. 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., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; 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, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, revision D.01; Gaussian, Inc.: Wallingford, CT, 2009.
63. Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields. J. Phys. Chem.1994, 98 (45), 11623–11627.
64. Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Phys. Rev. B1988, 37 (2), 785– 789.
65. Becke, A. D. Density‐functional Thermochemistry. III. The Role of Exact Exchange.
The Journal of Chemical Physics1993, 98 (7), 5648–5652.
66. Schäfer, A.; Huber, C.; Ahlrichs, R. Fully Optimized Contracted Gaussian Basis Sets of Triple Zeta Valence Quality for Atoms Li to Kr. The Journal of Chemical Physics1994,
100 (8), 5829–5835.
67. Schäfer, A.; Horn, H.; Ahlrichs, R. Fully Optimized Contracted Gaussian Basis Sets for Atoms Li to Kr. The Journal of Chemical Physics1992, 97 (4), 2571–2577.
68. (a) Gorelsky, S. I.; Lever, A. B. P. Electronic structure and spectra of ruthenium diimine complexes by density functional theory and INDO/S. Comparison of the two methods. J. Organomet. Chem. 2001, 635, 187. (b) Gorelsky, S. I. AOMix: Program for Molecular Orbital Analysis, revision 6.82; http://www.sg-chem.net, Ottawa, ON, 2013.