Skip to main content
SpringerLink
Log in

Theoretical study of spin–orbit coupling and zero-field splitting in the spin-forbidden two-state reaction between cobaltacyclopentadiene and isocyanate

  • Article
  • Physical Chemistry
  • Published:
Chinese Science Bulletin

Abstract

The two-state reaction mechanism of CpCo(C4H4) with isocyanate on the triplet and singlet potential energy surfaces has been investigated at the B3LYP level. A study is described for the computation of spin–orbit coupling of triplet state of the minimal energy crossing point (CP) with their singlet states and of the zero-field splitting (ZFS) parameters of the triplet states, including the full one- and two-electron terms of the Breit–Pauli Hamiltonian. There are two key crossing points along this two-state reaction pathway. The first crossing point—CP2 exists near 1B. The reacting system will change its spin multiplicity from the triplet state to the singlet state near this crossing region. Although the spin–orbit coupling interaction and ZFS D-tensor of the CP2 region are very strong, the reaction system will occur the reverse intersystem crossing from T1 to S0. Therefore, its spin-flip efficiency may be lower. The second crossing point, CP3 will again change its spin multiplicity from the singlet state to the triplet state in the Co–Cγ bond activation pathway, leading to a decrease in the barrier height of 1TS(CF) from 19.5 to 9.5 kcal/mol (1 cal = 4.182 J), and the efficiency of intersystem crossing from S0 to T1 is high because the larger spin–orbit coupling (SOC) matrix elements will result in the overpopulations of the three sublevels of T1 (3.30 × 10−1, 3.32 × 10−1, and 3.38 × 10−1, respectively).

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
Scheme 2
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Braunstein P, Nobel D (1989) Transition-metal-mediated reactions of organic isocyanates. Chem Rev 89:1927–1945

    Article  Google Scholar 

  2. Dazinger G, Schmid R, Kirchner K (2004) Mechanism of the ruthenium- catalyzed formation of pyrane-2-one and their sulfur and selen analogs from acetylene and CX2 (X = O, S, Se): a theoretical study. New J Chem 28:153–155

    Article  Google Scholar 

  3. Xie Y, Geng LN, Qu F et al (2009) Preparation and characterization of 3-(triethoxysilyl) propyl isocyanate self-assembled monolayer on surface of chip. Chin Sci Bull 54:738–742

    Article  Google Scholar 

  4. Wang QN, Yao ZG, Xu F et al (2012) Efficient synthesis of functionalized 2-pyridones by ytterbium chloride catalyzed tandem condensation. Chin Sci Bull 57:1612–1615

    Article  Google Scholar 

  5. Hong P, Yamazaki H (1977) Synthesis of 2-oxo-1,2-didydropridines by the reaction of cobaltacylopentadiene complexes with isocyanates. Synthesis 1:51–52

    Google Scholar 

  6. Wakatsuki Y, Yamazaki H (1976) Cobaltocene catalyzed synthesis of pyridines. Synthesis 1:26–27

    Article  Google Scholar 

  7. Dahy AA, Yamada K, Koga N (2009) Theoretical study on the reaction mechanism for the formation of 2-methylpyridine cobalt(i) complex from cobaltacyclopentadiene and acetonitrile. Organometallics 28:3636–3649

    Article  Google Scholar 

  8. Wang Y, Kumar D, Yang CL et al (2007) Theoretical study of N-demethylation of substituted N, N-dimethylanilines by cytochrome P450: the mechanistic significance of kinetic isotope effect profiles. J Phys Chem B 111:7700–7710

    Article  Google Scholar 

  9. Fiedler A, Schroder D, Shaik S et al (1994) Electronic structures and gas phase reactivities of cationic late-transition-metal oxides. J Am Chem Soc 116:10734–10741

    Article  Google Scholar 

  10. Lü LL, Wang XF, Zhu YC et al (2012) Theoretical study of spin-orbit coupling and intersystem crossing in the two-state reaction between Nb(NH2)3 and N2O. Sci China Chem 55:158–166

    Article  Google Scholar 

  11. Lü LL, Wang YC, Geng ZY et al (2009) Activation of C2 H6 by gas-phase Ta+: potential energy surfaces, spin–orbit coupling, spin-inversion probabilities, and reaction mechanisms. Organometallics 28:6160–6170

    Article  Google Scholar 

  12. Lü LL, Wang XF, Wang YC et al (2008) A theoretical study of the proton transfer proton transfer process in the spin-forbidden reaction 1HNO + OH−1→3NO−+H2O. Chin Sci Bull 53:1489–1496

    Article  Google Scholar 

  13. Lü LL, Wang YC, Wang Q et al (2010) Why is Pt4 + the least efficient cationic cluster in activating the C–H Bond in Methane? Two-state reaction computational investigation. J Phys Chem C 114:17610–17620

    Article  Google Scholar 

  14. Schroder D, Shaik S, Schwarz H (2000) Two-state reactivity as a new concept in organometallic chemistry. Acc Chem Res 33:139–145

    Article  Google Scholar 

  15. Hirao H, Kumar D, Que L et al (2006) Two-state reactivity in alkane hydroxylation by non-heme iron-oxo complexes. J Am Chem Soc 128:8590–8606

    Article  Google Scholar 

  16. Dalton DM, Oberg KM, Yu RT et al (2009) Enantioselective rhodium-catalyzed [2+2+2] cycloadditions of terminal alkynes and alkenyl isocyanates: mechanistic insights lead to a unified model that rationalizes product selectivity. J Am Chem Soc 131:15717–15728

    Article  Google Scholar 

  17. Agenet N, Gandon V, Vollhardt KPC et al (2007) Cobalt-catalyzed cyclotrimerization of alkynes: the answer to the puzzle of parallel reaction pathways. J Am Chem Soc 129:8860–8871

    Article  Google Scholar 

  18. Hong FE, Weng CM (2011) DFT studies on the reaction of CpCo(PPh3)2 with diphenylphosphinoalkynes: formation of cobaltacycles and cyclobutadiene-substituted CpCoCb diphosphines. Organometallics 30:3740–3748

    Article  Google Scholar 

  19. Harvey JN, Poli R, Smith KM (2003) Spin forbidden chemical reactions of transition metal compounds. New ideas and new computational challenges. Chem Soc Rev 32:1–8

    Article  Google Scholar 

  20. Frisch MJ (2003) Gaussian 03, Revision-E.01. Gaussian, Pittsburgh

    Google Scholar 

  21. Ditchfield R, Hehre WJ, Pople JA (1971) Self-consistent molecular-orbital methods. IX. An extended Gaussian-type basis for molecular-orbital studies of organic molecules. J Chem Phys 54:724–733

    Article  Google Scholar 

  22. Yoshizawa K, Shiota Y, Yamabe T (1999) Intrinsic reaction coordinate analysis of the conversion of methane to methanol by an iron-oxo species: a study of crossing seams of potential energy surfaces. J Chem Phys 111:538–544

    Article  Google Scholar 

  23. Harvey JN, Aschi M, Schwarz H et al (1998) The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces. Theor Chem Acc 99:95–99

    Article  Google Scholar 

  24. Hess BA, Marian CM, Wahlgren U et al (1996) A mean-field spin-orbit method applicable to correlated wavefunctions. Chem Phys Lett 251:365–371

    Article  Google Scholar 

  25. Neese F (2006) Importance of direct spin–spin coupling and spin-flip excitations for the zero-field splittings of transition metal complexes: a case study. J Am Chem Soc 128:10213–10222

    Article  Google Scholar 

  26. Lü LL, Zhu YC, Wang XF et al (2013) Spin-orbit coupling and zero-field splitting of the high-spin ferric enzyme-substrate complex: protocatechuate 3,4-dioxygenase complexed with 3,4-dihydroxyphenylacetate. Chin Sci Bull 58:627–633

    Article  Google Scholar 

  27. Neese F (2010) ORCA—An ab initio, density functional and semiempirical program package, Version 2.8. Max-Planck Institute for Bioinorganic Chemistry, Mülheim an der Ruhr

    Google Scholar 

  28. Harvey JN (2007) Understanding the kinetics of spin-forbidden chemical reaction. Phys Chem Chem Phys 9:331–343

    Article  Google Scholar 

  29. Koseki S, Fedorov DG, Schmidt MW et al (2001) Spin-orbit splittings in the third-row transition elements: comparison of effective nuclear charge and full breit–pauli calculations. J Phys Chem A 105:8262–8268

    Article  Google Scholar 

  30. Isobe H, Yamanaka S, Kuramitsu S et al (2008) Regulation mechanism of spin-orbit coupling in charge-transfer-induced luminescence of imidazopyrazinone derivatives. J Am Chem Soc 130:132–149

    Article  Google Scholar 

  31. Havlas Z, Downing JW, Michl J (1998) Spin–orbit coupling in biradicals. 2. Ab initio methodology and application to 1,1-biradicals: carbene and silylene. J Phys Chem A 102:5681–5692

    Article  Google Scholar 

  32. Schäfer A, Horn H, Ahlrichs R (1992) Fully optimized contracted gaussian basis sets for atoms Li to Kr. J Chem Phys 97:2571–2577

    Article  Google Scholar 

  33. Neese F, Solomon EI (1998) Calculation of zero-field splittings, g-values, and the relativistic nephelauxetic effect in transition metal complexes. Application to high-spin ferric complexes. Inorg Chem 37:6568–6582

    Article  Google Scholar 

  34. Levanon H, Norris JR (1978) The photoexcited triplet state and photosynthesis. Chem Rev 78:185

    Article  Google Scholar 

  35. Rozenshtein V, Berg A, Stavitski E et al (2005) Electron spin polarization of functionalized fullerences. Reversed quartet mechanism. J Phys Chem A 109:11144

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21263022), University Research Fund of Gansu Province Financial Department, and “QingLan” Talent Engineering Funds of Tianshui Normal University.

Author information

Authors and Affiliations

  1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui, 741001, China

    Lingling Lü, Xiaofang Wang, Yuancheng Zhu, Xinwen Liu & Kun Yuan

  2. College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, China

    Yongcheng Wang

Authors
  1. Lingling Lü
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaofang Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yuancheng Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xinwen Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kun Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yongcheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lingling Lü.

About this article

Cite this article

Lü, L., Wang, X., Zhu, Y. et al. Theoretical study of spin–orbit coupling and zero-field splitting in the spin-forbidden two-state reaction between cobaltacyclopentadiene and isocyanate. Chin. Sci. Bull. 59, 286–296 (2014). https://doi.org/10.1007/s11434-013-0024-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-013-0024-5

Keywords

Search

Navigation