Skip to main content
SpringerLink
Log in

Structural, electronic and reactivity studies on group 15 analogues of N-heterocyclic carbene

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

The present article reports density functional studies on the Group 15 analogues of N-heterocyclic carbene (NHC) on their structure, reactivity, stability and ligating properties. Long-range corrected density functionals have been used due to its recent success in predicting orbital energies. These ligands are found to have greater π-accepting ability than NHC. Electron-donating substituents have a dramatic effect on their stability as well as ligating properties. Furthermore, natural resonance theory (NRT) calculations have been performed to determine the percentage weighting of resonance contributing structures. In addition, density-based global reactivity descriptors such as chemical potential, hardness, electrophilicity index and softness are calculated using four different density functional methods, and compared with CCSD(T) results. Moreover, the density-based local reactivity descriptors are employed to study the reactivity of Group 15 analogues. From the plot of dual descriptors, it is found that the “ene” centre of the Group 15 analogues of NHC is pseudodual.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Arduengo AJ III, Harlow RL, Kline M (1991) J Am Chem Soc 113:361–363

    Article  CAS  Google Scholar 

  2. Melaimi M, Soleilhavoup M, Bertrand G (2010) Angew Chem Int Ed 49:8810–8849

    Article  CAS  Google Scholar 

  3. Hahn FE, Jahnke MC (2008) Angew Chem Int Ed 47:3122–3172

    Article  CAS  Google Scholar 

  4. Segawa Y, Yamashita M, Nozaki K (2006) Science 314:113–115

    Article  CAS  Google Scholar 

  5. Segawa Y, Yamashita M, Nozaki K (2009) J Am Chem Soc 131:9201–9203

    Article  CAS  Google Scholar 

  6. Schmidt ES, Jockisch A, Schmidbaur H (1999) J Am Chem Soc 121:9758–9759

    Article  CAS  Google Scholar 

  7. Yoo H, Carroll PJ, Berry DH (2006) J Am Chem Soc 128:6038–6039

    Article  CAS  Google Scholar 

  8. Herrmann WA, Denk M, Behm J, Scherer W, Klingan FR, Bock H, Solouki B (1992) Wagner. Angew Chem Int Ed Engl 31:1485–1488

    Article  Google Scholar 

  9. Pan B, Xu Z, Bezpalko MW, Foxman BM, Thomas CM (2012) Inorg Chem 51:4170–4179

    Article  CAS  Google Scholar 

  10. Day GS, Pan B, Kellenberger DL, Foxman BM, Thomas CM (2011) Chem Commun 47:3634–3636

    Article  CAS  Google Scholar 

  11. Heims F, Pfaff FF, Abram SLL, Farquhar ER, Bruschi M, Greco C, Ray K (2014) J Am Chem Soc 136:582–585

    Article  CAS  Google Scholar 

  12. Tulchinsky Y, Iron MA, Botoshansky M, Gandelman M (2011) Nat Chem 3:525–531

    Article  CAS  Google Scholar 

  13. Carmalt CJ, Lomeli V, McBurnett BG, Cowley AH (1997) Chem Commun 21:2095–2096

    Article  Google Scholar 

  14. Caputo CA, Jennings MC, Tuononen HM, Jones ND (2009) Organometallics 28:990–1000

    Article  CAS  Google Scholar 

  15. Denk MK, Gupta S, Ramachandran R (1996) Tetrahedron Lett 37:9025–9028

    Article  CAS  Google Scholar 

  16. Burck S, Daniels J, Gans-Eichler T, Gudat D, Nättinen K, Nieger M (2005) Z Anorg Allg Chem 631:1403–1412

    Article  CAS  Google Scholar 

  17. Denk MK, Gupta S, Lough AJ (1999) Eur J Inorg Chem 1999:41–49

    Article  Google Scholar 

  18. Boche G, Andrews P, Harms K, Marsch M, Rangappa KS, Schimeczek M, Willeke C (1996) J Am Chem Soc 118:4925–4930

    Article  CAS  Google Scholar 

  19. Gudat D, Haghverdi A, Hupfer H, Nieger M (2000) Chem Eur J 6:3414–3425

    Article  CAS  Google Scholar 

  20. Burck S, Gudat D, Nieger M, Benkö Z, Nyulászi L, Szieberth D (2009) Z Allg Anorg Chem 635:245–252

    Article  CAS  Google Scholar 

  21. Gudat D (2010) Acc Chem Res 43:1307–1316

    Article  CAS  Google Scholar 

  22. Gudat D, Haghverdi A, Nieger M (2000) Angew Chem Int Ed 39:3084–3086

    Article  CAS  Google Scholar 

  23. Schmid D, Loscher S, Gudat D, Bubrin D, Hartenbach I, Schleid T, Benkö Z, Nyulászi L (2009) Chem Commun 2009:830–832

    Article  Google Scholar 

  24. Burck S, Götz K, Kaupp M, Nieger M, Weber J (2009) Schmedt auf der Günne J, Gudat. J Am Chem Soc 131:10763–10774

    Article  CAS  Google Scholar 

  25. Benkö Z, Burck S, Gudat D, Hofmann M, Lissner F, Nyulászi L, Zenneck U (2010) Chem Eur J 16:2857–2865

    Article  CAS  Google Scholar 

  26. Gudat D, Kaaz M, Bender J, Förster D, Frey W, Nieger M (2013) Dalton Trans 43:680–689

    Google Scholar 

  27. Mourgas G, Nieger M, Förster D, Gudat D (2013) Inorg Chem 52:4104–4122

    Article  CAS  Google Scholar 

  28. Wilson DJD, Couchman SA, Dutton JL (2012) Inorg Chem 51:7657–7668

    Article  CAS  Google Scholar 

  29. Tuononen MH, Roesler R, Dutton JL, Ragogna PJ (2007) Inorg Chem 46:10693–10706

    Article  CAS  Google Scholar 

  30. Choudhury J (2011) Angew Chem Int Ed 50:10772–10774

    Article  CAS  Google Scholar 

  31. Alcarazo M, Stork T, Anoop A, Thiel W, Fürstner A (2010) Angew Chem Int Ed 49:2542–2546

    Article  CAS  Google Scholar 

  32. Guha AK, Sarmah S, Phukan AK (2010) Dalton Trans 39:7374–7383

    Article  CAS  Google Scholar 

  33. Hohenberg P, Kohn W (1964) Phys Rev 136:864–871

    Article  Google Scholar 

  34. Parr RG, Yang W (1989) Density functional theory for atoms and molecules. Oxford University Press, New York

    Google Scholar 

  35. Parr RG, Donnelly RA, Levy M, Palke WE (1978) J Chem Phys 68:3801–3807

    Article  CAS  Google Scholar 

  36. Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512–7516

    Article  CAS  Google Scholar 

  37. Yang W, Parr RG (1985) Proc Natl Acad Sci USA 82:6723–8726

    Article  CAS  Google Scholar 

  38. Koopmans TA (1933) Physica 104:1–6

    Google Scholar 

  39. Szabo A, Ostlund NS (1996) Modern quantum chemistry introduction to advanced electronic structure theory. Dover Publication, Inc, Mineola, New York

    Google Scholar 

  40. Parr RG, Yang W (1984) J Am Chem Soc 106:4049–4050

    Article  CAS  Google Scholar 

  41. Yang W, Mortier WJ (1986) J Am Chem Soc 108:5708–5711

    Article  CAS  Google Scholar 

  42. Morell C, Grand A, Toro-Labbé A (2005) J Phys Chem A 109:205–212

    Article  CAS  Google Scholar 

  43. Cárdenas C, Rabi N, Ayers PW, Morell C, Jaramillo P, Fuentealba P (2009) J Phys Chem A 113:8660–8667

    Article  CAS  Google Scholar 

  44. Parr RG, Szentpaly LV, Liu S (1999) J Am Chem Soc 121:1922–1924

    Article  CAS  Google Scholar 

  45. Chattaraj PK, Maiti B, Sarkar U (2003) J Phys Chem A 107:4973–4975

    Article  CAS  Google Scholar 

  46. Becke AD (1993) J Chem Phys 98:5648–5652

    Article  CAS  Google Scholar 

  47. Becke AD (1988) Phys Rev A 38:3098–3100

    Article  CAS  Google Scholar 

  48. Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789

    Article  CAS  Google Scholar 

  49. Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J Chem Phys 72:650–654

    Article  CAS  Google Scholar 

  50. McLean AD, Chandler GS (1980) J Chem Phys 72:5639–5648

    Article  CAS  Google Scholar 

  51. Iikura H, Tsuneda T, Yanai T, Hirao K (2001) J Chem Phys 115:3540–3544

    Article  CAS  Google Scholar 

  52. Yanai T, Tew DP, Handy NC (2004) Chem Phys Lett 393:51–57

    Article  CAS  Google Scholar 

  53. Chai JD, Gordon MH (2008) Phys Chem Chem Phys 10:6615–6620

    Article  CAS  Google Scholar 

  54. Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunga N, Nguyen KA, Su SJ, Windus TL, Dupuis M, Montgomery JA (1993) J Comput Chem 14:1347–1363

    Article  CAS  Google Scholar 

  55. Neese F (2008) ORCA-An ab initio, Density functional and semiempirical program package, version 3.0–35, University of Bonn, Bonn

  56. Glendening ED, Badenhoop JK, Reed AE, Carpenter JE, Bohmann JA, Morales CM, Landis CR, Weinhold F (2013) NBO 6.0, Theoretical chemistry Institute, University of Wisconsin, Madison

  57. Dixon DA, Arduengo AJ III (2006) J Phys Chem A 110:1968–1974

    Article  CAS  Google Scholar 

  58. Dixon DA, Gutowski M (2005) J Phys Chem A 109:5129–5135

    Article  CAS  Google Scholar 

  59. Nyulászi L, Veszprémi T, Forró A (2000) Phys Chem Chem Phys 2:3127–3129

    Article  Google Scholar 

  60. Kar R, Song JW, Hirao K (2013) J Comp Chem 34:958–964

    Article  CAS  Google Scholar 

  61. Glendening ED, Weinhold F (1998) J Comput Chem 19:593–609

    Article  CAS  Google Scholar 

  62. Glendening ED, Weinhold F (1998) J Comput Chem 19:610–627

    Article  CAS  Google Scholar 

  63. Glendening ED, Badenhoop JK, Weinhold F (1998) J Comput Chem 19:628–646

    Article  CAS  Google Scholar 

  64. Eichler TG, Gudat D, Nättinen K, Neiger M (2006) Chem Eur J 12:1162–1173

    Article  CAS  Google Scholar 

  65. Petz W, Kutschera C, Heitbaum M, Frenking G, Tonner R, Neumüller B (2005) Inorg Chem 44:1263–1274

    Article  CAS  Google Scholar 

  66. Tonner R, Frenking G (2008) Chem Eur J 14:3260–3272

    Article  CAS  Google Scholar 

  67. Tonner R, Frenking G (2008) Chem Eur J 14:3273–3289

    Article  CAS  Google Scholar 

  68. Tonner R, Frenking G (2009) Organometallics 28:3901–3905

    Article  CAS  Google Scholar 

  69. Tonner R, Frenking G (2009) Pure Appl Chem 81:597–614

    Google Scholar 

  70. Patel DS, Bharatam PV (2009) Chem Commun 2009:1064–1066

    Article  CAS  Google Scholar 

  71. Geerlings P, Proft FD, Langenaeker W (2003) Chem Rev 103:1793–1874

    Article  CAS  Google Scholar 

  72. Chattaraj PK, Sarkar U, Roy DR (2006) Chem Rev 106:2065–2091

    Article  CAS  Google Scholar 

  73. Geerlings P, Proft FD (2008) Phys Chem Chem Phys 10:3028–3042

    Article  CAS  Google Scholar 

  74. Oláh J, Proft FD, Veszprémi T, Geerlings P (2005) J Phys Chem A 109:1608–1615

    Article  CAS  Google Scholar 

  75. Oláh J, Veszprémi T, Proft FD, Geerlings P (2007) J Phys Chem A 111:10815–10823

    Article  CAS  Google Scholar 

  76. Correa JV, Jaque P, Oláh J, Labbé AT, Geerlings P (2009) Chem Phys Lett 470:180–186

    Article  CAS  Google Scholar 

  77. Kelemen Z, Hollóczki O, Oláh J, Nyulászi L (2013) RSC Adv 3:7970–7978

    Article  CAS  Google Scholar 

  78. Tsuneda T, Song JW, Suzuki S, Hirao K (2010) J Chem Phys 133:174101–174109

    Article  CAS  Google Scholar 

  79. Sjoberg P, Murray JS, Brink T, Politzer P (1990) Can J Chem 68:1440–1443

    Article  CAS  Google Scholar 

  80. Politzer P, Murray JS, Bulat FA (2010) J Mol Model 16:1731–1742

    Article  CAS  Google Scholar 

  81. Bulat FA, Burgess JS, Matis BR, Baldwin JW, Macaveiu L, Murray JS, Politzer P (2012) J Phys Chem A 116:8644–8652

    Article  CAS  Google Scholar 

  82. Kulshrestha P, Sukumar N, Murray JS, Giese RF, Wood TD (2009) J Phys Chem A 113:756–766

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work is dedicated to Dr. Sourav Pal on his 60th birthday. M. P. B thanks Council of Industrial and Scientific Research (CSIR), New Delhi, for financial assistance. RK thanks the SERB, Department of Science and Technology (DST), New Delhi for financial support [SB/FT/CS-132/2013]. The authors thank Netrakamal Bora for providing the optimized geometries for 2 and 3 with substituents CN, OH, NH 2 and OMe only.

Author information

Authors and Affiliations

  1. Department of Chemistry, Dibrugarh University, Dibrugarh, 786004, Assam, India

    Manash Protim Borpuzari, Ankur Kanti Guha & Rahul Kar

Authors
  1. Manash Protim Borpuzari
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ankur Kanti Guha
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rahul Kar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Rahul Kar.

Electronic supplementary material

Below is the link to the electronic supplementary material.

11224_2014_552_MOESM1_ESM.doc

Figures S1–S2, Tables S1–S2 and Cartesian coordinates of all the molecules are provided in supporting information. (DOC 2715 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Borpuzari, M.P., Guha, A.K. & Kar, R. Structural, electronic and reactivity studies on group 15 analogues of N-heterocyclic carbene. Struct Chem 26, 859–871 (2015). https://doi.org/10.1007/s11224-014-0552-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-014-0552-x

Keywords

Search

Navigation