Advertisement

Monatshefte für Chemie - Chemical Monthly

, Volume 141, Issue 6, pp 671–675 | Cite as

Formation of the silylene-bridged complex Fe2(CO)62-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

  • Van An Du
  • Gregor N. Stipicic
  • Maria Bendova
  • Ulrich SchubertEmail author
Original Paper

Abstract

Thermolysis of cis-Fe(CO)4(SiCl3)2 results in the formation of the novel compound Fe2(CO)62-SiCl2)3, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe2(CO)6(SiCl2)3, including CO dissociation and chlorine abstraction by a SiCl3 radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.

Graphical abstract

Keywords

Metal silyl complexes Homolytic bond cleavage Bridging silylene ligand DFT calculations 

Notes

Acknowledgments

This work was supported by Shell Corp., The Netherlands.

References

  1. 1.
    Derrien J, Chevrier J, Lethanh V, Mahan JE (1992) Appl Surf Sci 382:56Google Scholar
  2. 2.
    Huang H, Zybill CE, Luo L, Hieringer W, Huang HH (1998) Organometallics 7:5825CrossRefGoogle Scholar
  3. 3.
    Zybill CE, Huang W (1999) Inorg Chim Acta 291:380CrossRefGoogle Scholar
  4. 4.
    Du VA, Baumann SO, Stipicic GN, Schubert U (2009) Z Naturforsch B 64:1553Google Scholar
  5. 5.
    Simons RS, Tessier CA (1995) Acta Cryst C 51:1997CrossRefGoogle Scholar
  6. 6.
    Schmid G, Welz E (1979) Z Naturforsch B 34:929Google Scholar
  7. 7.
    Cotton FA, Troup JM (1974) J Chem Soc Dalton Trans 800Google Scholar
  8. 8.
    Scott AP, Radom L (1996) J Phys Chem 100:16502CrossRefGoogle Scholar
  9. 9.
    Pomeroy RK, Wijesekera KS (1980) Inorg Chem 19:3729CrossRefGoogle Scholar
  10. 10.
    Schubert U, Knorr M, Strasser C (1991) J Organomet Chem 411:75CrossRefGoogle Scholar
  11. 11.
    Bottoni A (1998) J Phys Chem A 102:10142CrossRefGoogle Scholar
  12. 12.
    Harvey NJ (2001) Spin-forbidden reactions in transition metal chemistry. In: Cundari TR (ed) Computational organometallic chemistry. Marcel Dekker, New York, p 291Google Scholar
  13. 13.
    Novak I, Huang W, Luo L, Huang HH, Ang HG, Zybill CE (1997) Organometallics 16:1567CrossRefGoogle Scholar
  14. 14.
    Becke AD (1988) Phys Rev A 38:3098CrossRefGoogle Scholar
  15. 15.
    Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785CrossRefGoogle Scholar
  16. 16.
    Alexander MV, Baker J, Pulay P (2003) J Chem Phys 118:7775CrossRefGoogle Scholar
  17. 17.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr JA, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, Revision C.02, Gaussian Inc Wallington CTGoogle Scholar
  18. 18.
    Schuchardt KL, Didier BT, Elsethagen T, Sun L, Gurumoorthi V, Chase J, Li J, Windus TL (2007) J Chem Inf Model 47:1045CrossRefGoogle Scholar
  19. 19.
    Sheldrick GM, SHELXS/L -97 (1997) Programs for crystal structure determination. University of Göttingen, Göttingen, GermanyGoogle Scholar

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Van An Du
    • 1
  • Gregor N. Stipicic
    • 2
  • Maria Bendova
    • 1
  • Ulrich Schubert
    • 1
    Email author
  1. 1.Institute of Materials ChemistryVienna University of TechnologyViennaAustria
  2. 2.Institute of Applied Synthetic ChemistryVienna University of TechnologyViennaAustria

Personalised recommendations