Anastasi, Anna E. and Deeth, Robert J.. (2009) Capturing the trans influence in low-spin d(8) square-planar platinum(II) systems using molecular mechanics. Journal Of Chemical Theory and Computation, Vol.5 (No.9). pp. 2339-2352. ISSN 1549-9618

Full text not available from this repository.

Abstract

Molecular modeling of coordination complexes continues to present challenges for force field methods. Implicit or explicit treatment of the significant d electron effects is mandatory. Ligand field molecular mechanics is designed for coordination complexes by explicitly including the ligand field stabilization energy (LFSE) and it is applied here to model the trans influence in tetracoordinate Pt-II complexes of general formulas PtX4, PtX3Y, cis-PtX2Y2, and trans-PtX2Y2, where X and Y are OH2, H-, Cl-, Br-, PR3, SH2, NR3, and pyridine. Parameters have been developed within the Merck molecular force field using DFT structures and energies as reference data. Both geometric changes and relative energies are generally well-reproduced although PH3 and H- complexes show deviations. However, for phosphine complexes, replacing PH3 with PMe3 resolves all bar one of these. The LFSE associated with the low-spin d(8) configuration ensures planar coordination and provides an electronic connection between all the ligands, thus enabling a correct description of the trans influence. The parameters developed for NR3 and PR3 with R = H work well for R = Me and Et and, in agreement with experimental and/or DFT structures, display either a tetrahedral distortion or even ligand dissociation.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Molecular structure, Platinum, Molecules -- Models, Transition metal complexes -- Structure, Ligand field theory
Journal or Publication Title:	Journal Of Chemical Theory and Computation
Publisher:	American Chemical Society
ISSN:	1549-9618
Date:	September 2009
Volume:	Vol.5
Number:	No.9
Number of Pages:	14
Page Range:	pp. 2339-2352
Identification Number:	10.1021/ct9001569
Status:	Peer Reviewed
Publication Status:	Published
Funder:	Engineering and Physical Sciences Research Council (EPSRC)
References:	(1) Pidcock, A.; Richards, R. E.; Venanzi, L. M. J. Chem. Soc. A 1966, 1707. (2) Mason, R.; McWeeny, R.; Towl, A. D. C. Faraday Discuss. 1969, 47, 20. (3) Pearson, R. G. Inorg. Chem. 1973, 12, 712–713. (4) Jorgensen, C. K. Inorg. Chem. 1964, 3, 1201–1202. (5) Harvey, J. N.; Heslop, K. M.; Orpen, A. G.; Pringle, P. G. Chem. Commun. 2003, 278–279. (6) Landis, C. R.; Cleveland, T.; Firman, T. K. J. Am. Chem. Soc. 1998, 120, 2641–2649. (7) Deeth, R. J.; Anastasi, A.; Diedrich, C.; Randell, K. Coord. Chem. ReV. 2009, 253, 795–816. (8) Bentz, A.; Comba, P.; Deeth, R. J.; Kerscher, M.; Seibold, B.; Wadepohl, H. Inorg. Chem. 2008, 47, 9518–9527. (9) Deeth, R. J.; Hearnshaw, L. J. A. Dalton Trans. 2006, 1092– 1100. (10) Deeth, R. J.; Foulis, D. L.; Williams-Hubbard, B. J. Dalton Trans. 2003, 3949–3955. (11) Baerends, E. J.; Autschbach, J.; Be´rces, A.; Bickelhaupt, F. M.; Bo, C.; Boerrigter, P. M.; Cavallo, L.; Chong, D. P.; Deng, L.; M., D. R.; E., E. D.; van Faassen, M.; Fan, L.; Fischer, T. H.; Fonseca Guerra, C.; van Gisbergen, S. J. A.; Groeneveld, J. A.; Gritsenko, O. V.; Gru¨ning, M.; Harris, F. E.; van den Hoek, P.; Jacob, C. R.; Jacobsen, H.; Jensen, L.; van Kessel, G.; Kootstra, F.; van Lenthe, E.; McCormack, D. A.; Michalak, A.; Neugebauer, J.; Nicu, V. P.; Osinga, V. P.; Patchkovskii, S.; Philipsen, P. H. T.; Post, D.; Pye, C. C.; Ravenek, W.; Ros, P.; Schipper, P. R. T.; Schreckenbach, G.; Snijders, J. G.; Sola`, M.; Swart, M.; Swerhone, D.; te Velde, G.; Vernooijs, P.; Versluis, L.; Visscher, L.; Visser, O.; Wang, F.; Wesolowski, T. A.; van Wezenbeek, E.; Wiesenekker, G.; Wolff, S. K.; Woo, T. K.; Yakovlev, A. L.; Ziegler, T. ADF2006.01; SCM, Theoretical Chemistry, Vrije Universiteit: Amsterdam, The Netherlands, 2006. (12) Guerra, C. F.; Snijders, J. G.; te Velde, G.; Baerends, E. J. Theor. Chem. Acc. 1998, 99, 391–403. (13) Van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1994, 101, 9783–9792. (14) Van Lenthe, E.; Baerends, E. J.; Snijders, J. G. J. Chem. Phys. 1993, 99, 4597–4610. (15) Pye, C. C.; Ziegler, T. Theor. Chem. Acc. 1999, 101, 396– 408. (16) Allinger, N. L.; Zhou, X. F.; Bergsma, J. J. Mol. Struct. 1994, 118, 69–83. (17) Bon, R. S.; van Vliet, B.; Sprenkels, N. E.; Schmitz, R. F.; de Kanter, F. J. J.; Stevens, C. V.; Swart, M.; Bickelhaupt, F. M.; Groen, M. B.; Orru, R. V. A. J. Org. Chem. 2005, 70, 3542–3553. (18) Fan, L. Y.; Ziegler, T. J. Phys. Chem. 1992, 96, 6937–6941. (19) Fan, L. Y.; Ziegler, T. J. Chem. Phys. 1992, 96, 9005–9012. (20) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J., J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; 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.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A.; Gaussian 03, ReVision C.02; Gaussian, Inc.: Wallingford CT, 2004. (21) Ehlers, A. W.; Bohme, M.; Dapprich, S.; Gobbi, A.; Hollwarth, A.; Jonas, V.; Kohler, K. F.; Stegmann, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993, 208, 111–114. (22) Bush, B. L.; Bayly, C. I.; Halgren, T. A. J. Comput. Chem. 1999, 20, 1495–1516. (23) Breneman, C. M.; Wiberg, K. B. J. Comput. Chem. 1990, 11, 361–373. (24) Deeth, R. J.; Fey, N.; Williams-Hubbard, B. J. J. Comput. Chem. 2005, 26, 123–130. (25) MOE, 2007 ed.; Chemical Computing Group, Montreal: Montreal, 2007. (26) Norrby, P. O.; Liljefors, T. J. Comput. Chem. 1998, 19, 1146– 1166. (27) Rappe, A. K.; Colwell, K. S.; Casewit, C. J. Inorg. Chem. 1993, 32, 3438–3450. (28) Root, D. M.; Landis, C. R.; Cleveland, T. J. Am. Chem. Soc. 1993, 115, 4201–4209. (29) Tubert-Brohman, I.; Schmid, M.; Meuwly, M. J. Chem. Theor. Comp. 2009, 5, 530–539. (30) Deeth, R. J.; Munslow, I. J.; Paget, V. J. NATO ASI Ser. 1997, 3/41, 77–103. (31) Brandt, P.; Norrby, T.; Akermark, E.; Norrby, P. O. Inorg. Chem. 1998, 37, 4120–4127. (32) Allured, V. S.; Kelly, C. M.; Landis, C. R. J. Am. Chem. Soc. 1991, 113, 1–12. (33) Cundari, T. R.; Fu, W.; Moody, E. W.; Slavin, L. L.; Snyder, L. A.; Sommerer, S. O.; Klinckman, T. R. J. Phys. Chem. 1996, 100, 18057–18064. (34) Burton, V. J.; Deeth, R. J.; Kemp, C. M.; Gilbert, P. J. J. Am. Chem. Soc. 1995, 117, 8407–8415. (35) Fletcher, D. A.; McMeeking, R. F.; Parkin, D. J. Chem. Inf. Comput. Sci. 1996, 36, 746–749. (36) Hocking, R. K.; Deeth, R. J.; Hambley, T. W. Inorg. Chem. 2007, 46, 8238–8244. (37) Coe, B. J.; Glenwright, S. J. Coord. Chem. ReV. 2000, 203, 5–80. (38) Lock, C. J. L.; Pilon, P. Acta Crystallogr., Sect. B 1981, 37, 45–49. (39) Packett, D. L.; Syed, A.; Trogler, W. C. Organometallics 1988, 7, 159–166. (40) Adams, R. D.; Barnard, T. S.; Li, Z. Y.; Zhang, L. J. Chem. Ber. Recl. 1997, 130, 729–733. (41) Russell, D. R.; Mazid, M. A.; Tucker, P. A. J. Chem. Soc., Dalton Trans. 1980, 1737–1742. (42) Annibale, G.; Bergamini, P.; Bertolasi, V.; Bortoluzzi, M.; Cattabriga, M.; Pitteri, B. Eur. J. Inorg. Chem. 2007, 5743– 5751. (43) Yam, V. W. W.; Tang, R. P. L.; Wong, K. M. C.; Lu, X. X.; Cheung, K. K.; Zhu, N. Y. Chem.sEur. J. 2002, 8, 4066– 4076. (44) Aldridge, S.; Coombs, D.; Jones, C. Acta Crystallogr., Sect. E 2003, 59, M584-M585. (45) Habereder, T.; Noth, H. Appl. Organomet. Chem. 2003, 17, 525–538. (46) Sivaramakrishna, A.; Su, H.; Moss, J. R. Acta Crystallogr., Sect. E 2007, 63, M244-M245. (47) Packett, D. L.; Jensen, C. M.; Cowan, R. L.; Strouse, C. E.; Trogler, W. C. Inorg. Chem. 1985, 24, 3578–3583. (48) Robertson, G. B.; Tucker, P. A.; Wickramasinghe, W. A. Aust. J. Chem. 1986, 39, 1495–1507. (49) Parkins, A. W.; Richard, C. J.; Steed, J. W. Inorg. Chim. Acta 2005, 358, 2827–2832. (50) Rath, N. P.; Fallis, K. A.; Anderson, G. K. Acta Crystallogr., Sect. C 1993, 49, 2079–2081. (51) Kozelka, J.; Luthi, H. P.; Dubler, E.; Kunz, R. W. Inorg. Chim. Acta 1984, 86, 155–163. (52) Deeth, R. J.; Randell, K. Inorg. Chem. 2008, 47, 7377–7388. (53) Wei, C. H.; Hingerty, B. E.; Busing, W. R. Acta Crystallogr., Sect. C 1989, 45, 26.
URI:	http://wrap.warwick.ac.uk/id/eprint/17381

Data sourced from Thomson Reuters' Web of Knowledge

Request changes to a record

Actions (login required)

View Item