Abstract
A series of ferrous-heme 2,6-dimethylphenyl isocyanide (DIMPI) and ferrous-heme mononitrosyl complexes have been synthesized and characterized. The heme portion of the complexes studied is varied with respect to the nature of the axial ligand, including complexes, where it is covalently tethered to the porphyrinate periphery. Reduced heme complexes, [(F8)FeII], [(PPy)FeII], [(PIm)FeII], and [(PImH)FeII], where F8 = tetrakis(2,6-difluorophenyl)-porphyrinate and PPy, PIm, and PImH are partially fluorinated tetraaryl porphyrinates with covalently appended axial base pyridyl/imidazolyl or histamine moieties, were employed; PImH is a new construct. Room temperature addition of DIMPI to these iron(II) complexes affords the bis-isocyanide species [(F8)FeII-(DIMPI)2] in the case of [(F8)FeII], while for the other hemes, mono-DIMPI compounds are obtained, [(PPy)FeII-(DIMPI)] [(2)-DIMPI], [(PIm)FeII-(DIMPI)] [(3)-DIMPI], and [(PImH)FeII-(DIMPI)] [(4)-DIMPI]. The structures of complexes (3)-DIMPI and (4)-DIMPI have been determined by single crystal X-ray crystallography, where interesting H…F(porphryinate aryl group) interactions are observed. 19F-NMR spectra determined for these complexes suggest that H…F(porphyrinate aryl groups) attractions also occur in solution, the H atom coming either from the DIMPI methyl groups or from a porphyinate axial base imidazole or porphyrinate pyrrole. Similarly, we have used nitrogen monoxide to generate ferrous-nitrosyl complexes, a five-coordinate species for F8, [(F8)FeII-(NO)], or low-spin six-coordinate compounds [(PPy)FeII-(NO)], [(PIm)FeII-(NO)], and [(PImH)FeII-(NO)]. The DIMPI and mononitrosyl complexes have also been characterized using UV–Vis, IR, 1H-NMR, and EPR spectroscopies.
Graphical abstract
Similar content being viewed by others
References
Ghosh A (ed) (2008) The smallest biomolecules: diatomics and their interactions with heme proteins. Elsevier, Amsterdam
Zhu Y, Silverman RB (2008) Biochemistry 47:2231–2243
Aono S (2008) Dalton Trans 3137–3146
Ohta T, Kitagawa T (2005) Inorg Chem 44:758–769
De Montellano PRO (2005) Cytochrome P-450: structure, mechanism, and biochemistry. Springer
Walker FA (2005) J Inorg Biochem 99:216–236
Zhao Y, Brandish PE, Ballou DP, Marletta MA (1999) Proc Natl Acad Sci USA 96:14753–14758
Poulos TL (2006) Curr Opin Struct Biol 16:736–743
Ford PC, Bandyopadhyay S, Lim MD, Lorkovic IM (2008) The smallest biomolecules: diatomics and their interactions with heme proteins. In: Ghosh A (ed) Elsevier, Amsterdam, pp 66–91
Tennyson AG, Lippard SJ (2011) Chem Biol 18:1211–1220
Traylor TG, Sharma VS (1992) Biochemistry 31:2847–2849
Schopfer MP, Wang J, Karlin KD (2010) Inorg Chem 49:6267–6282
Toledo JC Jr, Augusto O (2012) Chem Res Toxicol 25:975–989
Hunt AP, Lehnert N (2015) Acc Chem Res 48:2117–2125
Wilks A, Ikeda-Saito M (2014) Acc Chem Res 47:2291–2298
Matsui T, Unno M, Ikeda-Saito M (2010) Acc Chem Res 43:240–247
Schuller DJ, Wilks A, De Montellano PRO, Poulos TL (1999) Nat Struct Biol 6:860–867
Watkins CC, Boehning D, Kaplin AI, Rao M, Ferris CD, Snyder SH (2004) Proc Natl Acad Sci USA 101:2631–2635
Larsen RW, Mikšovská J (2007) Coord Chem Rev 251:1101–1127
Vos MH (2008) Biochim Biophys Acta 1777:15–31
Spiro TG, Soldatova AV, Balakrishnan G (2013) Coord Chem Rev 257:511–527
Vos MH, Liebl U (2015) Biochim Biophys Acta 1847:79–85
Liebl U, Lambry JC, Vos MH (2013) Biochim Biophys Acta 1834:1684–1692
Spiro TG, Wasbotten IH (2005) J Inorg Biochem 99:34–44
Bandyopadhyay D, Walda KN, Grogan TM, Magde D, Traylor TG, Sharma VS (1996) Biochemistry 35:1500–1505
Derbyshire ER, Marletta MA (2007) J Biol Chem 282:35741–35748
Evans JP, Kandel S, De Montellano PRO (2009) Biochemistry 48:8920–8928
Lucas HR, Karlin KD (2009) Metal Ions Life Sci 6:295–361
Blouin GC, Schweers RL, Olson JS (2010) Biochemistry 49:4987–4997
Blouin GC, Olson JS (2010) Biochemistry 49:4968–4976
Hematian S, Garcia-Bosch I, Karlin KD (2015) Acc Chem Res 48:2462–2474
Kim E, Helton ME, Wasser IM, Karlin KD, Lu S, Huang H-W, Moenne-Loccoz P, Incarvito CD, Rheingold AL, Honecker M, Kaderli S, Zuberbühler AD (2003) Proc Natl Acad Sci USA 100:3623–3628
Halime Z, Kieber-Emmons MT, Qayyum MF, Mondal B, Gandhi T, Puiu SC, Chufan EE, Sarjeant AAN, Hodgson KO, Hedman B, Solomon EI, Karlin KD (2010) Inorg Chem 49:3629–3645
Halime Z, Kotani H, Li Y, Fukuzumi S, Karlin KD (2011) Proc Natl Acad Sci USA 108:13990–13994
Kieber-Emmons MT, Qayyum MF, Li Y, Halime Z, Hodgson KO, Hedman B, Karlin KD, Solomon EI (2012) Angew Chem Int Ed 51:168–172
Garcia-Bosch I, Adam SM, Schaefer AW, Sharma SK, Peterson RL, Solomon EI, Karlin KD (2015) J Am Chem Soc 137:1032–1035
Li Y, Sharma SK, Karlin KD (2013) Polyhedron 58:190–196
Sharma SK, Rogler PJ, Karlin KD (2015) J Porphyrins Phthalocyanines 19:352–360
Schopfer MP, Mondal B, Lee D-H, Sarjeant AAN, Karlin KD (2009) J Am Chem Soc 131:11304–11305
Chufan EE, Puiu SC, Karlin KD (2007) Acc Chem Res 40:563–572
Ghiladi RA, Kretzer RM, Guzei I, Rheingold AL, Neuhold Y-M, Hatwell KR, Zuberbühler AD, Karlin KD (2001) Inorg Chem 40:5754–5767
Garcia-Bosch I, Sharma SK, Karlin KD (2013) J Am Chem Soc 135:16248–16251
Kim E, Shearer J, Lu S, Moeenne-Loccoz P, Helton ME, Kaderli S, Zuberbühler AD, Karlin KD (2004) J Am Chem Soc 126:12716–12717
Kamaraj K, Kim E, Galliker B, Zakharov LN, Rheingold AL, Zuberbühler AD, Karlin KD (2003) J Am Chem Soc 125:6028–6029
Wang J, Schopfer MP, Puiu SC, Sarjeant AAN, Karlin KD (2010) Inorg Chem 49:1404–1419
Berto TC, Praneeth VKK, Goodrich LE, Lehnert N (2009) J Am Chem Soc 131:17116–17126
Spek A (2009) Acta Crystallogr Sect D 65:148–155
Jameson GB, Ibers JA (1979) Inorg Chem 18:1200–1208
Kretzer RM, Ghiladi RA, Lebeau EL, Liang H-C, Karlin KD (2003) Inorg Chem 42:3016–3025
Song B, Yu B-S (2003) Bull Korean Chem Soc 24:981–985
Wood MA, Dickinson K, Willey GR, Dodd GH (1987) Biochem J 247:675–678
A reviewer suggested the bending may be due to a pseudo Jahn-Teller effect arising from a slight weakening of the Fe-N5(imidazole) bond in (3)-DIMPI compared to that in (4)-DIMPI (see Table 2); see Kitagawa T et al. (2005) J Phys Chem B 109: 21110-21117
Thompson DW, Kretzer RM, Lebeau EL, Scaltrito DV, Ghiladi RA, Lam K-C, Rheingold AL, Karlin KD, Meyer GJ (2003) Inorg Chem 42:5211–5218
Pauling L (1932) J Am Chem Soc 54:3570–3582
Shimoni L, Glusker JP (2015) In: Hargittai I, Hargittai B (eds) Science of crystal structures: highlights in crystallography. Springer International Publishing, Cham, pp 187–203
Kryachko E, Scheiner S (2004) J Phys Chem A 108:2527–2535
Rohde J-U, In J-H, Lim MH, Brennessel WW, Bukowski MR, Stubna A, Münck E, Nam W, Que L (2003) Science 299:1037–1039
England J, Guo Y, Farquhar ER, Young VG, Münck E, Que L (2010) J Am Chem Soc 132:8635–8644
As suggested by a reviewer, the room-temperature molecular structures for (3)-DIMPI and (4)-DIMPI may be dynamic with respect to Fe-C-N bending; the IR band observed for these complexes do seem to be asymmetric, and composed of two bands, possibly two conformers
Lehnert N, Scheidt WR, Wolf MW (2014) In: Mingos DMP (ed) Nitrosyl complexes in inorganic chemistry, biochemistry and medicine ii. Springer, New York, pp 155–223
Hayes RG, Ellison MK, Scheidt WR (2000) Inorg Chem 39:3665–3668
Wasser IM, Huang H-W, Moeenne-Loccoz P, Karlin KD (2005) J Am Chem Soc 127:3310–3320
Praneeth VKK, Neese F, Lehnert N (2005) Inorg Chem 44:2570–2572
Scheidt WR, Brinegar AC, Ferro EB, Kirner JF (1977) J Am Chem Soc 99:7315–7322
Acknowledgments
This work was supported by the National Institutes of Health (R01 GM 060353 to K.D.K).
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
Sharma, S.K., Kim, H., Rogler, P.J. et al. Isocyanide or nitrosyl complexation to hemes with varying tethered axial base ligand donors: synthesis and characterization. J Biol Inorg Chem 21, 729–743 (2016). https://doi.org/10.1007/s00775-016-1369-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00775-016-1369-4