Skip to main content
SpringerLink
Log in

Electronically Coupled MM Quadruple Bonded Complexes of Molybdenum and Tungsten

  • Chapter
  • First Online:
Metal-Metal Bonding

Part of the book series: Structure and Bonding ((STRUCTURE,volume 136))

Abstract

The synthesis, molecular and electronic structures of covalently linked dinuclear units having MM quadruple bonds (M = Mo or W) are described together with their attendant spectroscopies. Particular attention is paid to compounds where M2δ to bridge π bonding generates strongly coupled M2 centers whose mixed valence ions formed upon one electron oxidation traverse the Class II/III border.

In memory of Professor F.A. Cotton.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Cotton FA, Shang M (1991) The structure of the molybdenum tetranuclear cluster complex Mo4Cl8(PEt3)4: how unrecognized disorder previously reduced the quality of the refinement. J Cluster Sci 2:121–129

    Article  CAS  Google Scholar 

  2. McGinnis RN, Ryan TR, McCarley RE (1978) Reactions of activated quadruply bonded molybdenum dimers. Formation of new rectangular clusters containing the tetrametal analog of cyclobutadiyne. J Am Chem Soc 100:7900–7902

    CAS  Google Scholar 

  3. Ryan TR, McCarley RE (1982) Synthesis and characterization of rectangular tetranuclear cluster complexes of molybdenum(II) by condensation of quadruply bonded dimers. Inorg Chem 21:2072–2079

    Article  CAS  Google Scholar 

  4. Chisholm MH, MacIntosh AM (2005) Linking multiple bonds between metal atoms: clusters, dimers of “dimers”, and higher ordered assemblies. Chem Rev 105:2949–2976

    Article  CAS  Google Scholar 

  5. Cotton FA, Murillo CA, Walton RA (2005) Multiple bonds between metal atoms. Springer Science, Berlin, Germany

    Book  Google Scholar 

  6. Robin MB, Day P (1967) Mixed valence chemistry. a survey and classification. Adv Inorg Chem Radiochem 10:247–422

    CAS  Google Scholar 

  7. Cayton RH, Chisholm MH (1989) Electronically coupled bonding between covalently linked metal-metal quadruple bonds of molybdenum and tungsten. J Am Chem Soc 111:8921–8923

    Article  CAS  Google Scholar 

  8. Cayton RH, Chisholm MH, Lobkovsky EB (1991) Metal-metal multiple bonds in ordered assemblies. 1. Tetranuclear molybdenum and tungsten carboxylates involving covalently linked metal-metal quadruple bonds. Molecular models for subunits of one-dimensional stiff-chain polymers. J Am Chem Soc 113:8709–8724

    Article  CAS  Google Scholar 

  9. Cotton FA, Donahue JP, Murillo CA (2003) Polyunsaturated dicarboxylate tethers connecting dimolybdenum redox and chromophoric centers: syntheses, structures, and electrochemistry. J Am Chem Soc 125:5436–5450

    Article  CAS  Google Scholar 

  10. Cotton FA, Lin C, Murillo CA (1998) Coupling Mo2 n + units via dicarboxylate bridges. Dalton Trans 3151–3154

    Google Scholar 

  11. Cotton FA, Daniels LM, Lin C, Murillo CA (1999) Square and triangular arrays based on Mo2 4 + and Rh2 4 + units. J Am Chem Soc 121:4538–4539

    Article  CAS  Google Scholar 

  12. Cotton FA, Lin C, Murillo CA (2001) Supramolecular arrays based on dimetal building block. Acc Chem Res 34:759–771

    Article  CAS  Google Scholar 

  13. Cotton FA, Murillo CA, Villagrán D, Yu R (2006) Uniquely strong electronic communication between [Mo2] units linked by dioxolene dianions. J Am Chem Soc 128:3281–3290

    Article  CAS  Google Scholar 

  14. Cotton FA, Li Z, Lin CY, Murillo CA, Villagrán D (2006) Strong electronic interaction between two dimolybdenum units linked by tetraazatetracene. Inorg Chem 45:767–778

    Article  CAS  Google Scholar 

  15. Cotton FA, Lin CY, Murillo CA, Villagrán D, Wang X (2003) Modifying electronic communication in dimolybdenum units by linkage isomers of bridged oxamidate dianions. J Am Chem Soc 125:13564–13575

    Article  CAS  Google Scholar 

  16. Cayton RH, Chisholm MH, Huffman JC, Lobkowsky EB (1991) 1,8-Naphthyridinyl-2,7-dioxy bridged quadruply bonded molybdenum-molybdenum system, an insight into the nature of a linear rigid chain polymer [M-M…M-M]. Angew Chem Int Edit 30:862–864

    Article  Google Scholar 

  17. Chisholm MH, Clark RJH, Gallucci JC, Hadad CM, Patmore NJ (2004) Electronically-coupled tungsten-tungsten quadruple bonds: comparisons of electronic delocalization in 3,6-dioxypyradizine and oxalate bridged compounds. J Am Chem Soc 126:8303–8313

    Article  CAS  Google Scholar 

  18. Bursten BE, Chisholm MH, Clark RJH, Firth S, Hadad CM, MacIntosh AM, Wilson PJ, Woodward PM (2002) Oxalate bridged complexes of dimolybdenum and ditungsten supported by pivalate ligands: \({(\mathrm{t}\mbox{ -}{\mathrm{BuCO}}_{2})}_{3}{\mathrm{M}}_{2}(\mu \mbox{ -}{\mathrm{O}}_{2}{\mathrm{CCO}}_{2}){\mathrm{M}}_{2}{({\mathrm{O}}_{2}\mathrm{C}\mbox{ -}\mathrm{t}\mbox{ -}\mathrm{Bu})}_{3}\). Correlation of the solid-state, molecular and electronic structures with Raman, resonance Raman and electronic spectral data. J Am Chem Soc 124:3050–3063

    Article  CAS  Google Scholar 

  19. Bursten BE, Chisholm MH, Clark RJH, Firth S, Hadad CM, Wilson PJ, Woodward PM (2002) Perfluoroterephthalate bridged complexes with MM quadruple bonds: \({(\mathrm{t}\mbox{ -}{\mathrm{BuCO}}_{2})}_{3}{\mathrm{M}}_{2}(\mu \mbox{ -}{\mathrm{O}}_{2}{\mathrm{CC}}_{6}{\mathrm{F}}_{4}{\mathrm{CO}}_{2}){\mathrm{M}}_{2}{({\mathrm{O}}_{2}\mathrm{C}\mbox{ -}\mathrm{t}\mbox{ -}\mathrm{Bu})}_{3}\), where M = Mo or W. Studies of solid-state, molecular and electronic structure and correlations with electronic and Raman spectra data. J Am Chem Soc 124:12244–12254

    Article  CAS  Google Scholar 

  20. Cotton FA, Donahue JP, Murillo CA (2003) Polyunsaturated dicarboxylate tethers connecting dimolybdenum redox and chromophoric centers: absorption spectra and electronic structures. J Am Chem Soc 125:5486–5492

    Article  CAS  Google Scholar 

  21. Chisholm MH, Feil F, Hadad CM, Patmore NJ (2005) Electronically coupled MM quadruply-bonded complexes (M = Mo or W) employing terephthalate bridges: toward molecular rheostats and switches. J Am Chem Soc 127:18150–18158

    Article  CAS  Google Scholar 

  22. Byrnes MJ, Chisholm MH, Clark RJH, Gallucci JC, Hadad CM, Patmore NJ (2004) Thienylcarboxylate ligands bound to and bridging MM quadruple bonds, M = Mo or W: models for polythiophenes incorporating MM quadruple bonds. Inorg Chem 43:6334–6344

    Article  CAS  Google Scholar 

  23. Barybin MV, Chisholm MH, Dalal NS, Holovics TH, Patmore NJ, Robinson R, Zipse DJ (2005) Long range electronic coupling of MM quadruple bonds (M = Mo or W) via a 2,6-azulenedicarboxylate bridge. J Am Chem Soc 127:15182–15190

    Article  CAS  Google Scholar 

  24. Chisholm MH, Patmore NJ (2006) Electronic coupling in 1, 4 − (COS)2C6H4 linked MM quadruple bonds (M = Mo or W): the influence of S for O substitution. Dalton Trans 3164–3169

    Google Scholar 

  25. Chisholm MH, Singh N (2009) Are tetrathiooxalate and diborinate bridge MM quadruply bonded complexes related to oxalate bridged complexes? Dalton Trans 5867–5872

    Google Scholar 

  26. Chisholm MH, Patmore NJ (2007) Studies of electronic coupling and mixed valency in metal-metal quadruply bonded complexes linked by dicarboxylate and closely related ligands. Acc Chem Res 40:19–27

    Article  CAS  Google Scholar 

  27. Richardson DE, Taube H (1981) Determination of E2 ′-E′ in multistep charge transfer by stationary-electrode pulse and cyclic voltammetry: application to binuclear amines. Inorg Chem 20:1278–1285

    Article  CAS  Google Scholar 

  28. Bursten BE, Chisholm MH and D’Acchioli JS (2005) Oxalate bridged dinuclear M2 units: dimers of dimers, cyclotetramers (squares) and extended sheets [M = Mo, W, Tc, Ru and Rh]. Inorg Chem 44:8476–8480

    Article  Google Scholar 

  29. Chisholm MH, Patmore NJ (2009) Oxalate bridged heteronuclear compounds containing MM quadruple bonds (MM = Mo2 MoW and W2) and their radical cations. Can J Chem 87:1–7

    Article  Google Scholar 

  30. Cotton FA, Jin J-Y, Zhong L, Murillo CA, Reibenspies JH (2008) Exceptionally strong electronic coupling between [Mo2] units linked by substituted quinones. Chem Commun 211–213

    Google Scholar 

  31. Cotton FA, Donahue JP, Murillo CA, Perez LM, Yu R (2003) Cyclic polyamidato dianions as bridges between Mo2 4 + units. Synthesis, crystal structures, electrochemistry, absorption spectra and electronic structures. J Am Chem Soc 125:8900–8910

    Article  CAS  Google Scholar 

  32. Cotton FA, Murillo CA, Young MD, Yu R, Zhao Q (2008) Very large differences in electronic communication of dimetal species with heterobiphenylene and heteroanthracene units. Inorg Chem 47:219–229

    Article  CAS  Google Scholar 

  33. Chisholm MH, D’Acchioli JS, Pate BD, Patmore NJ, Dalal NS, Zipse DJ (2005) Cations \({\mathrm{M}}_{2}{({\mathrm{O}}_{2}\mathrm{C}\mbox{ -}\mathrm{t}\mbox{ -}\mathrm{Bu})}_{4}^{+}\), where M = Mo and W and \(\mathrm{MoW}{({\mathrm{O}}_{2}\mathrm{C}\mbox{ -}\mathrm{t}\mbox{ -}\mathrm{Bu})}_{4}^{+}\). Theoretical, spectroscopic and structural investigations. Inorg Chem 44:1061–1067

    Article  CAS  Google Scholar 

  34. Chisholm MH, Pate BD, Wilson PJ, Zalesk JM (2002) On the electronic delocalization in the radical cations formed by oxidation of MM quadruple bonds linked by oxalate and perfluoroterephthalate bridges. Chem Commun 1084–1085

    Google Scholar 

  35. Brunschwig BS, Creutz C, Sutin N (2002) Optical transitions of symmetrical mixed-valence systems in the class II-III transition regime. Chem Soc Rev 31:168–184

    Article  CAS  Google Scholar 

  36. Hush NS (1967) Intervalence-transfer absorption. II. Theoretical considerations and spectroscopic data. Progr Inorg Chem 8:381–444

    Google Scholar 

  37. Lear BJ, Chisholm MH (2009) Oxalate Bridged MM Quadruply Bonded Complexes as Test Beds for Current Mixed Valence Theory: Looking Beyond the IVCT Transition. Inorg Chem 48:10954–10971

    Article  CAS  Google Scholar 

  38. Burdzinski G-T, Chisholm MH, Chou P-T, Chou Y-H, Feil F, Gallucci JC, Ghosh Y, Gustafson TL, Ho M-L, Liu Y, Ramnauth R and Turro C (2008) The remarkable influence of the M2δ to thienyl π conjugation in oligothiophenes incorporating MM quadruple bonds. Proc Nat Acad Sci U S A 105:15247–15252

    Article  CAS  Google Scholar 

  39. Chisholm MH, Chou P-T, Chou Y-H, Ghosh Y, Gustafson TL, Ho M-L (2008) Preparations and photophysical properties of fused and non-fused thienyl bridged MM (M = Mo or W) quadruply bonded complexes. Inorg Chem 47:3415–3425

    Article  CAS  Google Scholar 

  40. Cotton FA, Murillo CA, Yu R (2006) An equilibrium between a loop and a triangle containing Mo2 4 + species and perfluorodicarboxylate linkers. Inorg Chim Acta 359:4811–4820

    Article  CAS  Google Scholar 

  41. Cotton FA, Murillo CA, Yu R (2006) Dynamic equilibrium between cyclic oligomers. Thermodynamic and structural characterization of a square and a triangle. Dalton Trans 3900–3905

    Google Scholar 

  42. Cotton FA, Liu CY, Murillo CA, Wang X (2006) Dimolybdenum-containing molecular triangles and squares with diamidate linkers: structural diversity and complexity. Inorg Chem 45:2619–2626

    Article  CAS  Google Scholar 

  43. Lent CS (2006) Quantum cellular antomata. Imperial College Press, London

    Google Scholar 

  44. Angaridis P, Berry JF, Cotton FA, Lei P, Lin C, Murillo CA, Villagrán D (2004) Dicarboxylato-bridged diruthenium units in two different oxidation states: the first step towards the synthesis of Creutz-Taube analogs with dinuclear Ru2 n + species. Inorg Chem Commun 7:9–13

    Article  CAS  Google Scholar 

  45. Angaridis P, Berry JF, Cotton FA, Murillo CA, Wang X (2003) Molecular squares with paramagnetic diruthenium corners: synthetic and structural challenges. J Am Chem Soc 125:10327–10334

    Article  CAS  Google Scholar 

  46. Cotton FA, Murillo CA, Lin C (2002) The use of dimetal building blocks in convergent synthesis of large array. Proc Nat Acad Sci U S A 99:4810–4813

    Article  CAS  Google Scholar 

  47. Cotton FA, Daniels LM, Lin C, Murillo CA, Y S-Y (2001) Supramolecular squares with Rh2 4 + corners. Dalton Trans 502–504

    Google Scholar 

  48. Cotton FA, Lin C, Murillo CA (2001) The first dirhodium-based supramolecular assemblies with interlocking lattices and double helices. Dalton Trans 499–501

    Google Scholar 

  49. Chen W-Z, Ren T (2006) Symmetric and unsymmetric “dumbells” of Ru2-alkynyl units via C-C bond formation reactions. Inorg Chem 45:9175–9177

    Article  CAS  Google Scholar 

  50. Xi B, Ren T (2009) Wire-like diruthenium σ-alkynyl compounds and charge mobility therein. Compt Rend Chim 12:321–331

    Article  CAS  Google Scholar 

  51. Xu G-L, Wang C-W, Ni Y-H, Goodson TG, Ren T (2005) Iterative synthesis of oligoynes capped by a Ru2(ap)4-terminus and their electrochemical and optical properties. Organometallic 24:3247–3254

    Article  CAS  Google Scholar 

  52. Hurst SK, Ren T (2002) Synthesis, characterization and electrochemistry of diruthenium complexes linked by aryl acetylide bridges. J Organomet Chem 660:1–5

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, The Ohio State University, Columbus, OH, 43210, USA

    Malcolm H. Chisholm

Authors
  1. Malcolm H. Chisholm
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Malcolm H. Chisholm .

Editor information

Editors and Affiliations

  1. Dept. Chemistry, Columbia University, Broadway 3000, New York, 10027, NY, USA

    Gerard Parkin

Rights and permissions

Reprints and permissions

Copyright information

© 2010 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Chisholm, M.H. (2010). Electronically Coupled MM Quadruple Bonded Complexes of Molybdenum and Tungsten. In: Parkin, G. (eds) Metal-Metal Bonding. Structure and Bonding, vol 136. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-05243-9_2

Download citation

Publish with us

Policies and ethics

Search

Navigation