Skip to main content
SpringerLink
Log in

Reactivities of d0 transition metal complexes toward oxygen: Synthetic and mechanistic studies

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

Transition metals such as Fe in porphyrin complexes are known to bind or react with O2, and such reactions are critical to many biological functions and catalytic oxidation using O2. The transition metals in these reactions often contain valence d electrons, and oxidation of metals is an important step. In recent years, reactions of O2 with d0 transition metal complexes such as Hf(NR2)4 (R = alkyl) have been used to make metal oxide thin films as insulating gate materials in new microelectronic devices. This feature article discusses our recent studies of such reactions and the formation of TiO2 thin films. In contrast to the reactions of many dn complexes where metals are often oxidized, reactions of d0 complexes such as Hf(NMe2)4 and Ta(NMe2)4(SiR3) with O2 usually lead to the oxidation of ligands, forming, e.g., -ONMe2 and -OSiR3 from -NMe2 and -SiR3 ligands, respectively. Mechanistic and theoretical studies of these reactions have revealed pathways in the formation of the metal oxide thin films as microelectronic materials.

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

Similar content being viewed by others

References

  1. Smith R C, Ma T, Hoilien N, Tsung L Y, Bevan M J, Colombo L, Roberts J, Campbell S A, Gladfelter W L. Chemical vapour deposition of the oxides of titanium, zirconium and hafnium for use as high-k materials in microelectronic devices. A carbon-free precursor for the synthesis of hafnium dioxide. Adv Mater Opt Electron, 2000, 10: 105–114

    Article  CAS  Google Scholar 

  2. Flynn L J. Intel announces new chip for small computers. The New York Times, 2008, March 3

  3. Feig A L, Lippard S J. Reactions of non-heme iron(II) centers with dioxygen in biology and chemistry. Chem Rev, 1994, 94: 759–805

    Article  CAS  Google Scholar 

  4. Klotz I M, Kurtz D M. Metal-dioxygen complexes: A perspective. Chem Rev, 1994, 94: 567–568

    Article  CAS  Google Scholar 

  5. Theopold K H, Reinaud O M, Blanchard S, Leelasubeharoen S, Hess A, Thyagarajan S. Toward benign synthesis via catalytic oxidations using dioxygen or nitrous oxide. ACS Symp Ser, 2002, 823: 75–85

    Article  CAS  Google Scholar 

  6. Labinger J A, Hart D W, Seibert W E, Schwartz J. Electrophilic cleavage of the carbon-zirconium(IV) bond. Comparison and contrast with other transition metal alkyl systems. J Am Chem Soc, 1975, 97: 3851–3852

    Article  CAS  Google Scholar 

  7. Blackburn T F, Labinger J A, Schwartz J. Hydrozirconation. IV. Oxidation of alkylzirconium(IV) complexes to alcohols. Tetrahedron Lett, 1975, 16: 3041–3044

    Article  Google Scholar 

  8. Lubben T V, Wolczanski P T. Reactivity of dioxygen with group 4A alkoxy alkyls: epoxidation via metal alkyl mediated oxygen atom transfer. J Am Chem Soc, 1985, 107: 701–703

    Article  CAS  Google Scholar 

  9. Tilley T D. Trimethylsilyl derivatives of bis(cyclopentadienyl)zirconium and -hafnium. Crystal structure of (η 5-C5H5)2Zr(SiMe3)(S2-CNEt2). Organometallics 1985, 4: 1452–1457

    Article  CAS  Google Scholar 

  10. Woods J B, Beach D B, Nygren C L, Xue Z -L. CVD of titanium oxide thin films from the reaction of tetrakis(dimethylamido)titanium with oxygen. Chem Vapor Deposition 2005, 11: 289–291

    Article  CAS  Google Scholar 

  11. Wang R, Zhang X H, Chen S J, Yu X, Wang C S, Beach D B, Wu Y D, Xue Z L. Reactions of d0 group 4 amides with dioxygen. Preparation of unusual oxo aminoxy complexes and theoretical studies of their formation. J Am Chem Soc, 2005, 127: 5204–5211

    Article  CAS  Google Scholar 

  12. Chen S J, Zhang X H, Yu X, Qiu H, Yap G P A, Guzei I A, Lin Z, Wu Y D, Xue Z L. Reaction of Ta(NMe2)5 with O2: Formation of aminoxy and unusual (aminomethyl)amide oxo complexes and theoretical studies of the mechanistic pathways. J Am Chem Soc, 2007, 129: 14408–14421

    Article  CAS  Google Scholar 

  13. Qiu H, Chen S J, Wang C S, Wu Y D, Guzei I A, Chen X-T, Xue Z L. Synthesis and characterization of siloxy, aminoxy, and oxo complexes from the reaction of a tantalum amide silyl complex with oxygen. Inorg Chem, 2009, 48: 3073–3079

    Article  CAS  Google Scholar 

  14. Wu Z, Cai H, Yu X, Blanton J R, Diminnie J B, Pan H J, Xue Z. Synthesis of tantalum(V) amido silyl complexes and the unexpected formation of (Me2N)3Ta(η 2-ONMe2)[OSi(SiMe3)3] from the reaction of (Me2N)4Ta[Si(SiMe3)3] with O2. Organometallics, 2002, 21: 3973–3978

    Article  CAS  Google Scholar 

  15. Chen T, Wu Z, Li L, Sorasaenee K R, Diminnie J B, Pan H, Guzei I A, Rheingold A L, Xue Z. Direct observation of an equilibrium between (ButCH2)2W(≡CBut)(SiButPh2) and (ButCH2)W(=CHBut)2(SiButPh2) and an unusual silyl migration. J Am Chem Soc, 1998, 120: 13519–13520

    Article  CAS  Google Scholar 

  16. Chen T, Zhang X H, Wang C, Chen S, Wu Z, Li L, Sorasaenee K R, Diminnie J B, Pan H, Guzei I A, Rheingold A L, Wu Y D, Xue Z. A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen. Organometallics, 2005, 24: 1214–1224

    Article  CAS  Google Scholar 

  17. Wagner C D, Riggs W M, Davis L E, Moulder J F. Handbook of X-ray Photoelectron Spectroscopy.Minnesota: Perkin-Elmer Corporation, 1979

    Google Scholar 

  18. N. N. Greenwood, A. Earnshaw, Chemistry of the Elements; 2nd ed.; Oxford: Butterworth Heinemann, 1997. 959

    Google Scholar 

  19. Chisholm M H, Hammond C E, Huffman J C. Tetrakisdimethylamidozirconium and its dimethylamido lithium adduct: Structures of [Zr-(NMe2)4]2 and Zr(NMe2)6Li2(thf)2. Polyhedron, 1988, 7: 2515–2520

    Article  CAS  Google Scholar 

  20. Harvey J N, Poli R, Smith K M. Understanding the reactivity of transition metal complexes involving multiple spin states. Coord Chem Res, 2003, 238–239, 347–361

  21. Olmstead M M, Power P P, Viggiano M. New class of σ-bonded aliphatic aza-macrocyclic complexes of transition metals: Synthesis and X-ray crystal structures of nitrogen-bridged [(TiN4C12H24)2] and the oxo-bridged species [(N4C12H25)TiOTi(N4C12H25)]. J Am Chem Soc, 1983, 105: 2927–2928

    Article  CAS  Google Scholar 

  22. Friedrich S, Gade L H, Edwards A J, McPartlin M. Structures, dynamics, and reactivity of tripodal amido ligands coordinated to TiIV centres. Chem. Ber, 1993, 126: 1797–1805

    Article  CAS  Google Scholar 

  23. Lintanf A, Mantoux A, Blanquet E, Djurado E. Elaboration of Ta2O5 thin films using electrostatic spray deposition for microelectronic applications. J Phys Chem C, 2007, 111: 5708–5714

    Article  CAS  Google Scholar 

  24. Kuraison T. (Nissan Motor, Japan). MISFETs with improved gate operation capability. Japan Patent 072310881995-08-29

  25. Zhang X H, Chen S J, Cai H, Im H J, Chen T, Yu X, Chen X, Lin Z, Wu Y D, Xue Z L. Unexpected formation of (dimethylaminomethylene) methylamide complexes from the reactions between metal chlorides and lithium dimethylamide. Organometallics 2008, 27: 1338–1341

    Article  CAS  Google Scholar 

  26. Tilley T D. In: Patai S, Rappoport Z. eds. The Silicon-Heteroatom Bond. New York: Wiley, 1991. Chapters 9 and 10

    Google Scholar 

  27. Eisen M S. In: Rappoport Z, Apeloig Y. eds. The Chemistry of Organic Silicon Compounds, Vol. 2; New York: Wiley. 1998. Pt. 3, 2037

    Chapter  Google Scholar 

  28. Xue Z, Li L, Hoyt L K, Diminnie J B, Pollitte J L. Early-transition-metal silyl complexes free from anionic. pi.-Ligands. A new family of alkyl, alkylidene, and alkylidyne compounds. J Am Chem Soc, 1994, 116: 2169–2170

    Article  CAS  Google Scholar 

  29. McAlexander L H, Hung M, Li L, Diminnie J B, Xue Z, Yap G P A, Rheingold A L. Alkyl-silyl complexes free of anionic π ligands. Synthesis and characterization of (Me3ECH2)3MSi(SiMe3)3. Organometallics, 1996, 15: 5231–5235

    Article  CAS  Google Scholar 

  30. Li L, Diminnie J B, Liu X, Pollitte J L, Xue Z. Synthesis and characterization of (Me3ECH2)2Ta(=CHEMe3)Si(SiMe3)3 (E = C, Si). Kinetic and mechanistic studies of the formation of a silyl alkylidene complex through preferential silane elimination. Organometallics, 1996, 15: 3520–3527

    Article  CAS  Google Scholar 

  31. Diminnie J B, Xue Z. Reactions of alkyl alkylidene complexes with silanes. Synthesis and characterization of novel tantalum 1,1-metallasilacyclobutadiene and disilyl-substituted alkylidene complexes. J Am Chem Soc, 1997, 119: 12657–12658

    Article  CAS  Google Scholar 

  32. Wu Z, Diminnie J B, Xue Z. Synthesis and X-ray crystal structure of a chlorobis(trimethylsiloxy)zirconium silyl derivative, (Me3SiO)2Zr (SiPh2But)Cl·2THF. Organometallics 1998, 17: 2917–2920

    Article  CAS  Google Scholar 

  33. Wu Z, McAlexander L H, Diminnie J B, Xue Z. Reactions of (Me3ECH2)3ZrSi(SiMe3)3 (E = C, Si) with 2,6-dimethylphenyl isocyanide. Preferential isocyanide insertion into Zr-Silyl bonds. Organometallics, 1998, 17: 4853–4860

    Article  CAS  Google Scholar 

  34. Wu Z Z, Diminnie J B, Xue Z L. d0 Bis(silyl) complexes free of anionic π-ligands: Syntheses, structures, and a novel exchange between silyl ligands and silyl anions. J Am Chem Soc, 1999, 121: 4300–4301

    Article  CAS  Google Scholar 

  35. Yu X H, Cai H, Guzei I A, Xue Z L. Unusual equilibria involving group 4 amides, silyl complexes, and silyl anions via ligand exchange reactions. J Am Chem Soc, 2004, 126: 4472–4473

    Article  CAS  Google Scholar 

  36. Qiu H, Cai H, Woods J B, Wu Z, Chen T, Yu X H, Xue Z L. Disilyl complexes of zirconium, hafnium, and tantalum. Their synthesis, characterization, and exchanges with silyl anions. Organometallics, 2005, 24: 4190–4197

    Article  CAS  Google Scholar 

  37. Choi S H, Lin Z, Xue Z. Theoretical studies of the ralative stabilities of transition metal alkylidyne (CH3)2M(≡CH)(X) and bis(alkylidene) (CH3)M(≡CH2)2(X). Organometallics, 1999, 18: 5488–5495

    Article  CAS  Google Scholar 

  38. Nugent W A, Mayer J M. Metal-Ligand Multiple Bonds. New York: Wiley, 1988

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, The University of Tennessee, Knoxville, TN, 37996-1600, USA

    ShuJian Chen & ZiLing Xue

  2. Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong, China

    XinHao Zhang, ZhenYang Lin & YunDong Wu

Authors
  1. ShuJian Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. XinHao Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. ZhenYang Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. YunDong Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. ZiLing Xue
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to ZhenYang Lin, YunDong Wu or ZiLing Xue.

Additional information

Supported by the U.S. National Science Foundation (CHE-051692), Research Grants Council of Hong Kong, and the British Royal Society Kan Tong Po Visiting Professorship Program.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chen, S., Zhang, X., Lin, Z. et al. Reactivities of d0 transition metal complexes toward oxygen: Synthetic and mechanistic studies. Sci. China Ser. B-Chem. 52, 1723–1733 (2009). https://doi.org/10.1007/s11426-009-0253-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-009-0253-2

Keywords

Search

Navigation