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Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels

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Abstract

Coupling of a local triplet carbene with a local triplet nitrene through an acetylene linkage gives a new brand of high spin quintet minima (\( {\text{X}}{-}\mathop {\text{C}}\limits^{ \cdot \cdot }{-}{\text{C}} \equiv {\text{C}}{-}\mathop {\text{N}}\limits_{ \cdot \cdot }^{ \cdot \cdot } \), where X = H, F, Cl, Br), which are rather experimentally unreachable. Placing the same linkage between the local open-shell singlet carbene (σ1π1) and the local triplet nitrene (π1π1) gives triplet minima which are 54–56 kcal/mol more stable than their corresponding quintets. The carbenic angles in both quintets and triplets follow electropositivity of X (H > Br > Cl > F), with every divalent angle in quintet being smaller than the corresponding one in the triplet. Finally no reactive intermediate is observed through connecting singlet states of carbene and nitrene subunits which gives a neutral linear molecule with X–C≡C–C≡N formula, and show about 70 kcal/mol more stability than the corresponding triplet states. Our results are compared at B3LYP, HF, MP2, MP4(SDTQ), CCSD(T), and QCISD(T) levels using 6-311++G** basis set.

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References

  1. Borden WT (ed) (1982) Diradicals. Wiley, New York

    Google Scholar 

  2. Zuev PS, Sheridan RS (1995) Tetrahedron 51:11337

    Article  CAS  Google Scholar 

  3. Nicolaides A, Nakayama T, Yamazaki K, Tomioka H, Koseki S, Stracener LL, McMahon RJ (1999) J Am Chem Soc 121:10563

    Article  CAS  Google Scholar 

  4. Inagaki S, Iwase K, Goto N (1986) J Org Chem 51:362

    Article  CAS  Google Scholar 

  5. Enyo T, Arai N, Nakane N, Nicolaides A, Tomioka H (2005) J Org Chem 70:7744

    Article  CAS  Google Scholar 

  6. Flock M, Pierloot K, Nguyen MT, Vanquickenborne LG (2000) J Phys Chem A 104:4022

    Article  CAS  Google Scholar 

  7. Nicolaides A, Enyo T, Miura D, Tomioka H (2001) J Am Chem Soc 123:2628

    Article  CAS  Google Scholar 

  8. Ling C, Minato M, Lahti PM, Willigent Hv (1992) J Am Chem Soc 114:9959

    Article  CAS  Google Scholar 

  9. Enyo T, Nicolaides A, Tomioka H (2002) J Org Chem 67:5578

    Article  CAS  Google Scholar 

  10. Borden WT, Davidson ER (1981) Acc Chem Res 14:69

    Article  CAS  Google Scholar 

  11. Dougherty DA (1991) Acc Chem Res 24:88

    Article  CAS  Google Scholar 

  12. Itoh K (1967) Chem Phys Lett 1:235

    Article  CAS  Google Scholar 

  13. Wasserman E, Murray RW, Yager WA, Trozzolo AM, Smolinsky G (1967) J Am Chem Soc 89:5076

    Article  CAS  Google Scholar 

  14. Iwamura H (1990) Adv Phys Org Chem 26:179

    Article  CAS  Google Scholar 

  15. Subhan W, Rempala P, Sheridan RS (1998) J Am Chem Soc 120:11528

    Article  CAS  Google Scholar 

  16. Zuev PS, Sheridan RS (1993) J Am Chem Soc 115:3788

    Article  CAS  Google Scholar 

  17. Zuev PS, Sheridan RS (1994) J Am Chem Soc 116:9381

    Article  CAS  Google Scholar 

  18. Tomioka H, Komatsu K, Nakayama T, Shimizu M (1993) Chem Lett 22:1291

    Article  Google Scholar 

  19. Nicolaides A, Tomioka H, Murata S (1998) J Am Chem Soc 120:11530

    Article  CAS  Google Scholar 

  20. Kassaee MZ, Haerizade BN, Arshadi S (2003) J Mol Struct (THEOCHEM) 639:187

    Article  CAS  Google Scholar 

  21. Kassaee MZ, Sayyed-Alangi SZ, Hossaini Z (2004) J Mol Struct (THEOCHEM) 676:7

    Article  CAS  Google Scholar 

  22. Kassaee MZ, Hossaini ZS, Haerizade BN, Sayyed-Alangi SZ (2004) J Mol Struct (THEOCHEM) 681:129

    Article  CAS  Google Scholar 

  23. Kassaee MZ, Musavi SM, Ghambarian M, Buazar F (2005) J Mol Struct (THEOCHEM) 726:171

    Article  CAS  Google Scholar 

  24. Kassaee MZ, Musavi SM, Buazar F (2005) J Mol Struct (Theochem) 728:15

    Article  CAS  Google Scholar 

  25. Kassaee MZ, Musavi SM, Jalalimanesh N (2008) JTCC 7:1

    Google Scholar 

  26. Frisch MJ, Head-Gordon M, Pople JA (1990) Chem Phys Lett 166:281

    Article  CAS  Google Scholar 

  27. Becke AD (1996) J Chem Phys 104:1040

    Article  CAS  Google Scholar 

  28. Adamo C, Barone V (1997) Chem Phys Lett 274:242

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  30. Pople JA, Krishnan R (1978) Int J Quant Chem 14:91

    Article  Google Scholar 

  31. Krishnan R, Frisch MJ, Pople JA (1980) J Chem Phys 72:4244

    Article  CAS  Google Scholar 

  32. Pople JA, Head-Gordon M, Raghavachari K (1987) J Chem Phys 87:5968

    Article  CAS  Google Scholar 

  33. Scuseria GE, Schaefer HF III (1989) J Chem Phys 90:3700

    Article  CAS  Google Scholar 

  34. Hout RF, Levi BA, Heher WJ (1985) J Comput Chem 82:234

    Google Scholar 

  35. Defrees DJ, McLean AD (1985) J Chem Phys 82:333

    Article  CAS  Google Scholar 

  36. Carpenter JE, Weinhold F (1988) J Mol Struct (THEOCHEM) 41:169

    Google Scholar 

  37. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski Jr. VG, Montgomery JA, Stratmann RE, Burant JC, Dapprich S, Millan JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelly C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Gonzalez C, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian 98. Gaussian Inc., Pittsburgh, PA

  38. Barrientos C, Redondo P, Largo A (2000) J Phys Chem A 104:11541

    Article  CAS  Google Scholar 

  39. Barrientos C, Cimas A, Largo A (2001) J Phys Chem A 105:6724

    Article  CAS  Google Scholar 

  40. Apeloig Y, Pauncz R, Karni M, West R, Steiner W, Chapman D (2003) Organometallics 22:3250

    Article  CAS  Google Scholar 

Download references

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Authors and Affiliations

  1. Department of Chemistry, Tarbiat Modares University, P.O. Box 14155-175, Tehran, Iran

    M. Z. Kassaee, S. Soleimani-Amiri, M. Majdi & S. M. Musavi

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  1. M. Z. Kassaee
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  2. S. Soleimani-Amiri
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  3. M. Majdi
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  4. S. M. Musavi
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Correspondence to M. Z. Kassaee.

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Kassaee, M.Z., Soleimani-Amiri, S., Majdi, M. et al. Novel quintet and triplet (nitrenoethynyl)halomethylenes at theoretical levels. Struct Chem 21, 229–235 (2010). https://doi.org/10.1007/s11224-009-9568-z

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