Abstract
In the last decades, density functional theory has become unavoidable in theoretical studies of organometallic chemistry. Most of the recent functionals contain many parameters that are adjusted using carefully chosen reaction sets. However, these sets only contain a few entries involving late transition metal reaction, so that choosing a functional for such a study is difficult. In this work, the theoretical description of the oxidative addition of \(\hbox {Pd}(\hbox {PH}_3)_2\) to 2-iodo-allyl-aniline was chosen as a representative reaction of palladium. The competitive binding of the palladium to the alkene or the nitrogen atom was used to assess the accuracy of ab initio methods (MP2, MP3, MP2.5, SCS-MP2, SCS-MP3) and 56 functionals ranging from local density approximation to the costly double-hybrid approaches (such as B2PLYP), against a CCSD(T)/CBS reference value. Model systems \([(\hbox {PH}_3)_2\hbox {ClPd}(\hbox {NH}_3)]^{+}\) and \([(\hbox {PH}_3)_2\hbox {ClPd}(\hbox {H}_2\hbox {C}=\hbox {CH}_2)]^{+}\) were first considered: all functionals correctly predict that the azane complex is the most stable. However, some functionals overestimate its stability compared to the alkene complex. This is amplified in the 2-iodo-allyl-aniline study: SCS-MP3, B2PLYP as well as BP86, most of the meta-GGA (generalized gradient approximation), hybrid GGAs and hybrid meta-GGAs are predicting that oxidative addition proceeds directly. On the contrary, many functionals, among which B3LYP, M06-2X and most range-separated methods, wrongly predict that palladium first binds to the nitrogen atom before proceeding to the olefin insertion. Resorting to these functionals to study inorganic reactions with palladium might thus result in predicting wrong mechanisms.
Similar content being viewed by others
Notes
It is worth noting that, according to our ISI Web of Science analysis, the BP86 functional is used in 8 % of the articles dealing with late TM but only to 2 % of the articles resorting to DFT in general.
The name of each functional used in this work was searched in journal titles and abstracts from ISI Web of Science (December 27, 2013) for articles published during the 2008–2013 period. According to these data, B3LYP still represents more than 50 % of the references. This remains true even if the search is limited to articles dealing with late transition metals only.
Beware that this corresponds to: \(0.5 E_X^{HF} + 0.5 E_X^{LSDA} + E_C^{LYP}\).
This corresponds to: \( 0.5 E_X^{HF} + 0.5 E_X^{LSDA} + 0.5 \Delta E_X^{B88} + E_C^{LYP}\).
References
Dedieu A (2000) Chem Rev 100(2):543. doi:10.1021/cr980407a
Ziegler T, Autschbach J (2005) Chem Rev 105(6):2695. doi:10.1021/cr0307188
Balcells D, Clot E, Eisenstein O (2010) Chem Rev 110(2):749. doi:10.1021/cr900315k
García-Melchor M, Braga AAC, Lledós A, Ujaque G, Maseras F (2013) Acc Chem Res 46(11):2626. doi:10.1021/ar400080r
Cramer CJ, Truhlar DG (2009) Phys Chem Chem Phys 11(46):10757. doi:10.1039/b907148b
Tsuji J (2005) Palladium reagents and catalysts. Wiley, New York. doi:10.1002/0470021209
Becke AD (1988) Phys Rev A 38:3098
Perdew JP (1986) Phys Rev B 33(12):8822
Deubel DV, Ziegler T (2002) Organometallics 21(8):1603. doi:10.1021/om010662c
Deubel DV, Ziegler T (2002) Organometallics 21(21):4432. doi:10.1021/om0202975
Peverati R, Truhlar DG (2012) Phys Chem Chem Phys 14(38):13171. doi:10.1039/c2cp42025b
Heck RF, Nolley JP (1972) J Org Chem 37(14):2320. doi:10.1021/jo00979a024
Mizoroki T, Mori K, Ozaki A (1971) Bull Chem Soc Jpn 44(2):581
Yamamura M, Moritani I, Murahashi SI (1975) J Organomet Chem 91(2):C39. doi:10.1016/S0022-328X(00)89636-9
King AO, Okukado N, Negishi EI (1977) J Chem Soc Chem Commun 19:683. doi:10.1039/C39770000683
Milstein D, Stille JK (1978) J Am Chem Soc 100(11):3636. doi:10.1021/ja00479a077
Miyaura N, Suzuki A (1979) J Chem Soc Chem Commun 19:866. doi:10.1039/C39790000866
Johnson LK, Killian CM, Brookhart M (1995) J Am Chem Soc 117(23):6414. doi:10.1021/ja00128a054
Ittel SD, Johnson LK, Brookhart M (2000) Chem Rev 100(4):1169. doi:10.1021/cr9804644
Mecking S (2000) Coord Chem Rev 203(1):325. doi:10.1016/S0010-8545(99)00229-5
Fernández I, Solé D, Sierra MA (2011) J Org Chem 76(6):1592. doi:10.1021/jo1020954
Solé D, Mariani F, Fernández I, Sierra MA (2012) J Org Chem 77(22):10272. doi:10.1021/jo301924e
Stephens PJ, Devlin FJ, Chabalowski CF, Frisch MJ (1994) J Phys Chem 98(45):11623. doi:10.1021/j100096a001
Chéron N, Jacquemin D, Fleurat-Lessard P (2012) Phys Chem Chem Phys 14(19):7170. doi:10.1039/C2CP40438A
Gadzhiev OB, Ignatov SK, Razuvaev AG, Masunov AE (2009) J Phys Chem A 113(32):9092. doi:10.1021/jp900484s
Gadzhiev OB, Ignatov SK, Gangopadhyay S, Masunov AE, Petrov AI (2011) J Chem Theory Comput 7(7):2021. doi:10.1021/ct100754m
Gadzhiev OB, de la Rosa LAG, Meléndez-Bustamante FJ, de Parrodi CA, Abdallah HH, Petrov AI, Scior T (2012) J Phys Org Chem 25(11):971. doi:10.1002/poc.2985
Lu L, Hu H, Hou H, Wang B (2013) Comput Theor Chem 1015:64. doi:10.1016/j.comptc.2013.04.009
Sousa SF, Fernandes PA, Ramos MJ (2007) J Phys Chem A 111(42):10439. doi:10.1021/jp0734474
Lai W, Yao J, Shaik S, Chen H (2012) J Chem Theory Comput 8(9):2991. doi:10.1021/ct3005936
Ikeda A, Nakao Y, Sato H, Sakaki S (2007) J Phys Chem A 111(30):7124. doi:10.1021/jp0708648
Averkiev BB, Zhao Y, Truhlar DG (2010) J Mol Cat A 324(1–2):80. doi:10.1016/j.molcata.2010.03.016
Steinmetz M, Grimme S (2013) ChemistryOpen 2(3):115. doi:10.1002/open.201300012
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, AustinAJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, FoxDJ (2009) Gaussian 09 Revision D.01. Gaussian Inc., Wallingford
Møller C, Plesset MS (1934) Phys Rev 46:618
Sedlak R, Riley KE, Rězáč J, Pitoňák M, Hobza P (2013) ChemPhysChem 14(4):698. doi:10.1002/cphc.201200850
Antony J, Grimme S (2007) J Phys Chem A 111(22):4862. doi:10.1021/jp070589p
Takatani T, Sherrill CD (2007) Phys Chem Chem Phys 9(46):6106. doi:10.1039/B709669K
Grimme S (2003) J Comput Chem 24(13):1529. doi:10.1002/jcc.10320
Purvis GD III, Bartlett RJ (1982) J Chem Phys 76:1910
Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479. doi:10.1016/S0009-2614(89)87395-6
Hohenberg P, Kohn W (1964) Phys Rev 136(3B):B864. doi:10.1103/PhysRev.136.B864
Vosko SJ, Wilk L, Nusair M (1980) Can J Phys 58:1200
Perdew JP, Burke K, Ernzerhof M (1996) Phys Rev Lett 77:3865
Handy NC, Cohen AJ (2001) Mol Phys 99:403
Lee C, Yand W, Parr R (1988) Phys Rev B 37:785
Perdew JP, Wang Y (1992) Phys Rev B 45:13244
Boese AD, Handy NC (2001) J Chem Phys 114(13):5497. doi:10.1063/1.1347371
Peverati R, Zhao Y, Truhlar DG (2011) J Phys Chem Lett 2(16):1991. doi:10.1021/jz200616w
Peverati R, Truhlar DG (2012) J Chem Theory Comput 8(7):2310. doi:10.1021/ct3002656
Tao JM, Perdew JP, Staroverov VN, Scuseria GE (2003) Phys Rev Lett 91:146401
Zhao Y, Truhlar DG (2006) J Chem Phys 125:194101
Zhao Y, Truhlar DG (2008) Acc Chem Res 41:157
Peverati R, Truhlar DG (2012) J Phys Chem Lett 3(1):117. doi:10.1021/jz201525m
Cohen AJ, Handy NC (2001) Mol Phys 99:607
Boese AD, Handy NC (2002) J Chem Phys 116:9559
Becke AD (1993) J Chem Phys 98:5648
Adamo C, Barone V (1998) J Chem Phys 108:664
Hamprecht FA, Cohen A, Tozer DJ, Handy NC (1998) J Chem Phys 109:6264
Wilson PJ, Bradley TJ, Tozer DJ (2001) J Chem Phys 115:9233
Xu X, Goddard WA III (2004) Proc Natl Acad Sci USA 101:2673
Becke AD (1997) J Chem Phys 107:8554
Schmider HL, Becke AD (1998) J Chem Phys 108:9624
Austin A, Petersson GA, Frisch MJ, Dobek FJ, Scalmani G, Throssell K (2012) J Chem Theory Comput 8(12):4989. doi:10.1021/ct300778e
Adamo C, Barone V (1999) J Chem Phys 110:6158
Lynch BJ, Fast PL, Harris M, Truhlar DG (2000) J Phys Chem A 104(21):4811. doi:10.1021/jp000497z
Peverati R, Truhlar DG (2011) J Chem Phys 135(19):191102. doi:10.1063/1.3663871
Zhao Y, Truhlar DG (2008) Theor Chem Acc 120:215
Becke AD (1996) J Chem Phys 104:1040
Zhao Y, Truhlar DG (2004) J Phys Chem A 108:6908
Boese AD, Martin JML (2004) J Chem Phys 121:3405
Zhao Y, Truhlar DG (2006) J Phys Chem A 110:13126
Chai JD, Head-Gordon M (2008) J Chem Phys 128:084106
Chai JD, Head-Gordon M (2008) Phys Chem Chem Phys 10:6615
Peverati R, Truhlar DG (2011) J Phys Chem Lett 2(21):2810. doi:10.1021/jz201170d
Henderson TM, Izmaylov AF, Scuseria GE, Savin A (2008) J Chem Theory Comput 4(8):1254. doi:10.1021/ct800149y
Henderson TM, Izmaylov AF, Scalmani G, Scuseria GE (2009) J Chem Phys 131:044108. doi:10.1063/1.3185673
Peverati R, Truhlar DG (2012) Phys Chem Chem Phys 14(47):16187. doi:10.1039/c2cp42576a
Yanai T, Tew D, Handy N (2004) Chem Phys Lett 393:51
Iikura H, Tsuneda T, Yanai T, Hirao K (2001) J Chem Phys 115:3540
Grimme S (2006) J Chem Phys 124:034108. doi:10.1063/1.2148954
Schwabe T, Grimme S (2006) Phys Chem Chem Phys 8(38):4398. doi:10.1039/B608478H
Karton A, Tarnopolsky A, Lamère JF, Schatz GC, Martin JML (2008) J Phys Chem A 112(50):12868. doi:10.1021/jp801805p
Grimme S (2006) J Comput Chem 27:1787
Grimme S, Ehrlich S, Goerigk L (2011) J Comput Chem 32(7):1456. doi:10.1002/jcc.21759
Goerigk L, Grimme S (2011) J Chem Theory Comput 7(2):291. doi:10.1021/ct100466k
Peterson K, Figgen D, Dolg M, Stoll H (2007) J Chem Phys 126:124101
Peterson KA, Shepler BC, Figgen D, Stoll H (2006) J Phys Chem A 110:13877
Hay P, Wadt W (1985) J Chem Phys 82:299
Ehlers A, Böhme M, Dapprich S, Gobbi A, Höllwarth A, Jonas V, Köhler K, Stegmann R, Veldkamp A, Frenking G (1993) Chem Phys Lett 208(1–2):111. doi:10.1016/0009-2614(93)80086-5
Roy L, Hay P, Martin R (2008) J Chem Theory Comput 4:1029
Check C, Faust T, Bailey J, Wright B, Gilbert T, Sunderlin L (2001) J Phys Chem A 105:8111
Feller D (1996) J Comp Chem 17:1571
Schuchardt KL, Didier BT, Elsethagen T, Sun L, Gurumoorthi V, Chase J, Li J, Windus TL (2007) J Chem Inf Model 47:1045. doi:10.1021/ci600510j
de Jong GT, Solà M, Visscher L, Bickelhaupt FM (2004) J Chem Phys 121(20):9982. doi:10.1063/1.1792151
de Jong GT, Bickelhaupt FM (2006) J Chem Theory Comput 2(2):322. doi:10.1021/ct050254g
Boys S, Bernardi F (1970) Mol Phys 19:553
Halkier A, Klopper W, Helgaker T, Jorgensen P, Taylor P (1999) J Chem Phys 111:9157
Mentel ŁM, Baerends EJ (2014) J Chem Theory Comput 10(1):252. doi:10.1021/ct400990u
Jurečka P, Hobza P (2002) Chem Phys Lett 365:89
Tarnopolsky A, Karton A, Sertchook R, Vuzman D, Martin JML (2008) J Phys Chem A 112(1):3. doi:10.1021/jp710179r
Gráfová L, Pitoňák M, Rězáč J, Hobza P (2010) J Chem Theory Comput 6(8):2365. doi:10.1021/ct1002253
Bento AP, Solaca M, Bickelhaupt FM (2008) J Chem Theory Comput 4:929
Perdew JP, Ruzsinszky A, Constantin LA, Sun J, Csonka GI (2009) J Chem Theory Comput 5:902
Garrec J, Sautet P, Fleurat-Lessard P (2011) J Phys Chem B 115(26):8545. doi:10.1021/jp200565w
Seth M, Ziegler T, Steinmetz M, Grimme S (2013) J Chem Theory Comput 9(5):2286. doi:10.1021/ct301112m
Burke K, Perdew JP, Ernzerhof M (1997) Int J Quant Chem 61(2):287. doi:10.1002/(SICI)1097-461X(1997)61:2<287::AID-QUA11>3.0.CO;2-9
Shamov GA, Schreckenbach G, Budzelaar PHM (2010) J Chem Theory Comput 6(11):3442. doi:10.1021/ct100389d
Solé D, Vallverdú L, Solans X, Font-Bardía M, Bonjoch J (2003) J Am Chem Soc 125(6):1587. doi:10.1021/ja029114w
Solé D, Vallverdú L, Solans X, Font-Bardia M, Bonjoch J (2004) Organometallics 23(6):1438. doi:10.1021/om034270c
Quintal MM, Karton A, Iron MA, Boese AD, Martin JML (2006) J Phys Chem A 110(2):709. doi:10.1021/jp054449w
Acknowledgments
This work was granted access to the HPC resources of IDRIS under the allocations 2012-070609 and 2013-070609 made by GENCI (Grand Équipement National de Calcul Intensif). This work has been achieved partially thanks to the resources of PSMN (Pôle Scientifique de Modélisation Numérique).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Grüber, R., Fleurat-Lessard, P. Performance of recent density functionals to discriminate between olefin and nitrogen binding to palladium. Theor Chem Acc 133, 1533 (2014). https://doi.org/10.1007/s00214-014-1533-2
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-014-1533-2