Abstract
Although density functional theory (DFT) provides a generally good description of transition metal systems, we have identified several cases, involving Fe(III) porphyrins and related systems, where common functionals fail to correctly describe the energetics of the different low-lying spin states. The question of metal- versus ligand-centered oxidation in high-valent transition metal complexes is also a challenging one for DFT calculations, as I have tried to illustrate with examples from among porphyrin, corrole, biliverdine, and NO complexes. In a number of cases, I have compared results obtained with different exchange–correlation functionals; in addition, I have added a discussion on the relative performance of pure versus hybrid functionals. Finally, I have offered some thoughts on the role that traditional wavefunction-based ab initio methods, now essentially absent from the bioinorganic arena, might play in the future.
References
Noodleman L, Lovell T, Han WG, Li J, Himo F (2004) Chem Rev 104:459–508
Friesner RA, Guallar V (2005) Ann Rev Phys Chem 56:389–427
Shaik S, de Visser SP (2005) In: Ortiz de Montellano PR (ed) Cytochrome P450: structure, mechanism, and biochemistry, 3rd edn. Kluwer/Plenum, New York, pp 45–85
Bassan A, Blomberg MRA, Borowski T, Siegbahn PEM (2006) J Inorg Biochem 100:727–743
Ghosh A, Taylor PR (2003) Curr Opin Chem Biol 7:113–124
Ghosh A, Steene E (2001) J Biol Inorg Chem 6:739–752
Ghosh A, Vangberg T, Gonzalez E, Taylor P (2001) J Porphyrins Phthalocyanines 5:345–356
Ghosh A, Persson BJ, Taylor PR (2003) J Biol Inorg Chem 8:507–511
Ghosh A, Taylor PR (2005) J Chem Theory Comput 1:597–600
Roos B (1999) Acc Chem Res 32:137–144
Ghosh A (2006) J Inorg Biochem 100:419–420
Ghosh A, Almlöf J, Que L (1994) J Phys Chem A 98:5576–5579
Ghosh A, Almlöf J, Que L (1996) Angew Chem Int Ed Engl 35:770–772
Becke AD (2003) J Chem Phys 119:2972–2977
Green MT (2001) J Am Chem Soc 123:9218–9219
Derat E, Shaik S (2006) J Am Chem Soc 128 (in press). DOI 10.1021/ja0600734
Green MT, Dawson JH, Gray HB (2004) Science 304:1653–1656
Stone KL, Hoffart LM, Behan RK, Krebs C, Green MT (2006) J Am Chem Soc 128:5100, 6147–6153
Horner O, Oddou J-L, Mouesca J-M, Houve JM (2006) J Inorg Biochem 100:477–479
Groves JT (2006) J Inorg Biochem 100:434–447
Conradie J, Wasbotten I, Ghosh A (2006) J Inorg Biochem 100:502–506
Ghosh A, Tangen E, Ryeng H, Taylor PR (2004) Eur J Inorg Chem 4555–4560
Decker A, Clay MD, Solomon EI (2006) J Inorg Biochem 100:697–706
Conradie MM, Conradie J, Ghosh A (2006) J Inorg Biochem 100:707–715
Chanda A, Popescu D-L, Tiago de Oliveira F, Bominaar EL, Ryabov AD, Münck E, Collins TJ (2006) J Inorg Biochem 100:606–619
Conradie MM, Conradie J, Ghosh A (2006) J Inorg Biochem 100:620–626
Ghosh A, Wondimagegn T, Parusel ABJ (2000) J Am Chem Soc 122:5100–5104
Steene E, Dey A, Ghosh A (2003) J Am Chem Soc 125:16300–16309
Fox JP, Ramdhanie B, Zareba AA, Czernuszewicz RS, Goldberg DP (2004) Inorg Chem 43:6600–6608
van Oort B, Tangen E, Ghosh A (2004) Eur J Inorg Chem 2442–2445
Wasbotten I, Ghosh A (2006) Inorg Chem 45:4914–4921
Ghosh A, Wondimagegn T, Ryeng H (2001) Curr Opin Chem Biol 5:744–750
Wondimagegn T, Ghosh A (2001) J Am Chem Soc 123:1543–1544
Shima S, Thauer RK (2005) Curr Opin Microbiol 8:643–648
Pelmenschikov V, Blomberg MRA, Siegbahn PEM, Crabtree RH (2002) J Am Chem Soc 124:4039–4049
Jensen KP, Ryde U (2003) J Phys Chem A 107:7539–7545
Hinderberger D, Piskorski RP, Goenrich M, Thauer RK, Schweiger A, Harmer J, Jaun B (2006) Angew Chem Int Ed Engl 45:3602–3607
Schultz NE, Zhao Y, Truhlar DG (2005) J Phys Chem A 109:11127–11143
Gill PMW (2001) Aust J Chem 54:661–662
Ghosh A, Gonzalez E (2006) Isr J Chem 40:1–8
De Angelis F, Jin N, Car R, Groves JT (2006) Inorg Chem 45:4268–4276
Handy NC, Cohen AJ (2001) Mol Phys 99:403–412
Baerends EJ, Gritsenko OV (2005) J Chem Phys 123:062202
Grabowski S, Hirata S, Ivanov S, Bartlett RJ (2002) J Chem Phys 116:4415–4425
Grimme S (2006) J Chem Phys 124:034108
Friesner RA, Knoll EH, Cao Y (2006) J Chem Phys (in press)
Cai S, Walker FA, Licoccia S (2000) Inorg Chem 39:3466–3478
Zakharieva O, Schunemann V, Gerdan M, Licoccia S, Cai S, Walker FA, Trautwein AX (2002) J Am Chem Soc 124:6636–6648
Walker FA, Licoccia S, Paolesse R (2006) J Inorg Biochem 100:810–837
Steene E, Wondimagegn T, Ghosh A (2001) J Phys Chem B 105:11406–11413. Addition/Correction: Steene E, Wondimagegn T, Ghosh A (2002) J Phys Chem B 106:5312–5312
Nardis S, Paolesse R, Licoccia S, Fronczek FR, Vicente MGH, Shokhireva TK, Cai S, Walker FA (2005) Inorg Chem 44:7030–7046
Vogel E, Will S, Tilling AS, Neumann L, Lex J, Bill E, Trautwein AX, Wieghardt K (1994) Angew Chem Int Ed Engl 33:731–735
Gross Z, Gray HB (2006) Comments Inorg Chem 27:61–72
Nguyen KT, Rath SP, Latos-Grazynski L, Olmstead MM, Balch AL (2004) J Am Chem Soc 126:6210–6211
Harischandra DN, Zhang R, Newcomb M (2005) J Am Chem Soc 127:13776–13777
Aliaga-Alcalde M, George SD, Mienert B, Bill E, Wieghardt K, Neese F (2005) Angew Chem Int Ed Engl 44:2908–2912
Newcomb M, Zhang R, Chandrasena REP, Halgrimson JA, Horner JH, Makris TM, Sligar SG (2006) J Am Chem Soc 128:4580–4581
Dey A, Ghosh A (2002) J Am Chem Soc 124:3206–3207
Berry JF, Bill E, Bothe E, George SD, Mienert B, Neese F, Wieghardt K (2006) Science (in press)
Ghosh A (2005) Acc Chem Res 38:943–954
Franzen S (2002) Proc Natl Acad Sci USA 99:16754–16759
Praneeth VKK, Haupt E, Lehnert N (2005) J Inorg Biochem 99: 940–948. Correction: Praneeth VKK, Haupt E, Lehnert N (2005) J Inorg Biochem 99: 1744–1744
Scheidt WR, Duval HF, Neal TJ, Ellison MK (2000) J Am Chem Soc 122:4651–4659
Ghosh A, Wondimagegn T (2000) J Am Chem Soc 122:8101–8102
Westcott BL, Enemark JL (1999) In: Solomon EI, Lever ABP (eds) Inorganic electronic structure and spectroscopy, vol 2. Wiley, New York, pp 403–450
Tangen E, Svadberg A, Ghosh A (2005) Inorg Chem 44:7802–7805
Serres RG, Grapperhaus CA, Bothe E, Bill E, Weyhermüller T, Neese F, Wieghardt K (2004) J Am Chem Soc 126:5138–5153
Zhang Y, Pavlosky MA, Brown CA, Westre TE, Hedman B, Hodgson KO, Solomon EI (1992) J Am Chem Soc 114:9189–9191
Ray M, Golombek AP, Hendrich MP, Yap GPA, Liable-Sands LM, Rheingold AL, Borovik AS (1999) Inorg Chem 38:3110–3115
Ray M, Golombek AP, Hendrich MP, Young VG, Borovik AS (1996) J Am Chem Soc 118:6084–6085
Tangen E, Ghosh A (2005) J Inorg Biochem 99:959–962
Koch H, de Meras AS, Pedersen TB (2003) J Chem Phys 118:9481–9484
Chong DP, Gritsenko OV, Baerends EJ (2002) J Chem Phys 116:1760–1772
Bartlett RJ, Lotrich VF, Schweigert IV (2005) J Chem Phys 123:062205
Baerends EJ, Gritsenko OV (1997) J Phys Chem A 101:5383–5403
Gritsenko OV, Baerends EJ (2004) J Chem Phys 120:8364–8372
Hoffmann R (1998) J Mol Struct (THEOCHEM) 424:1–6
Altun A, Guallar V, Friesner RA, Shaik S, Thiel W (2006) J Am Chem Soc 128:3924–3925
Conradie J, Ghosh A (2006) Inorg Chem 45:4902–4909
Acknowledgements
Much of the newer work described herein was carried out by my coworkers Ingar Wasbotten, Jeanet Conradie, and Espen Tangen. In addition, I thank Peter Taylor, Björn Roos, Evert Jan Baerends, Per Siegbahn, Richard Friesner, Stephen Lippard and Thomas Pedersen for stimulating discussions. The Research Council of Norway is thanked for generous financial support for the last several years.
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Ghosh, A. Transition metal spin state energetics and noninnocent systems: challenges for DFT in the bioinorganic arena. J Biol Inorg Chem 11, 712–724 (2006). https://doi.org/10.1007/s00775-006-0135-4
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DOI: https://doi.org/10.1007/s00775-006-0135-4