Skip to main content
SpringerLink
Log in

Diphosphine Substitution and Carbyne Ligand Transfer in the Reaction of 2,3-Bis(diphenylphosphino)maleic Anhydride (bma) with the Methylidyne-capped Clusters HCCo2MCp(CO)8 (where M=Mo, W): Synthesis and X-ray Diffraction Structures of the Vinylidene-bridged Clusters Co2MCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)]

  • Original Paper
  • Published:
Journal of Chemical Crystallography Aims and scope Submit manuscript

Abstract

Thermolysis of mixed-metal tetrahedrane cluster HCCo2MoCp(CO)8 (1) with the diphosphine ligand 2,3–bis(diphenylphosphino)maleic anhydride (bma) furnishes the cluster compounds HCCo2MoCp(CO)6[trans-2,3-bis(diphenylphosphino)succinic anhydride] (2), HCCo2MoCp(CO)6(bma) (3), and Co2MoCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)] (4) in low yields (<13%). The tungsten congener HCCo2WCp(CO)8 (5) reacts with bma to give Co2WCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)] (6) as the sole isolable product in 3% yield. The new clusters have been fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures of the vinylidene-bridged clusters 4 and 6 established by X-ray crystallography. Clusters 4 and 6 each contain 48e- and exhibit triangular Co2M cores, with a vinylidene moiety that caps one of the Co2M faces. The reactivity differences exhibited by clusters 1 and 5 with bma are contrasted with similar data from the substitution reaction of bma with the related cluster compounds PhCCo2MoCp(CO)8 and PhCCo2WCp(CO)8.

Index Abstract

The mixed-metal cluster HCCo2MoCp(CO)8 (1) reacts with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) at elevated temperature to afford the new clusters HCCo2MoCp(CO)6[trans-2,3-bis(diphenylphosphino)succinic anhydride] (2), HCCo2MoCp(CO)6(bma) (3), and Co2MoCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)] (4). Thermolysis of HCCo2WCp(CO)8 (5) with bma furnishes only Co2WCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)] (6) in trace amounts. The presence of the face-capping vinylidene ligand in clusters 4 and 6 has been confirmed by spectroscopic methods and X-ray crystallography.

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
Scheme 2
Fig. 1

Similar content being viewed by others

References

  1. Yang K, Smith JM, Bott SG, Richmond MG (1993) Organometallics 12:4779

    Article  CAS  Google Scholar 

  2. For a report on the synthesis and reactivity of PhCCo3(CO)7(bpcd), see: Bott SG, Shen H, Richmond MG (2001) Struct Chem 12:225

  3. For the first report involving the bridge-to-chelate isomerization of a diphosphine ligand at a metal cluster and the subsequent kinetics investigation, see: (a) Churchill MR, Lashewycz RA, Shapley JR, Richter SI (1980) Inorg Chem 19:1277 (b) Kandala S, Richmond MG (2006) Inorg Chem 45:5976

  4. For other documented phosphine ligand isomerizations about a metal cluster, see: (a) Evans J, Gracey BP, Gray LR, Webster M (1982) J Organomet Chem 240:61 (b) Puga J, Arce A, Braga D, Centritto N, Grepioni F, Castillo R, Ascanio (1987) J Inorg Chem 26:867 (c) Laurenczy G, Bondietti G, Ros R, Roulet R (1996) Inorg Chim Acta 247:65 (d) Adams RD, Captain B, Fu W, Pellechia PJ (2003) Inorg Chem 42:3111 (e) Watson WH, Wu G, Richmond MG (2005) Organometallics 24:5431 and references therein

  5. (a) Cotton FA, Hanson BE (1980) In: de Mayo P (ed) Rearrangements in ground and excited states. Academic Press, New York (Chapter 12) (b) Adams RD, Cotton FA (1973) J Am Chem Soc 95:6589

  6. Watson WH, Bodige SG, Ejsmont K, Liu J, Richmond MG (2006) J Organomet Chem 691:3609

    Article  CAS  Google Scholar 

  7. Bott SG, Yang K, Richmond MG (2006) J Organomet Chem 691:3771

    Article  CAS  Google Scholar 

  8. Zhang W, Watson WH, Richmond MG (2008) J Chem Crystallogr 38:9

    Article  CAS  Google Scholar 

  9. For related Co2Mo tetrahedral clusters containing a diphosphine ligand, see: (a) Bott SG, Yang K, Huang SH, Richmond MG (2004) J Chem Crystallogr 34:883 (b) Watson WH, Poola B, Richmond MG (2006) J Organomet Chem 691:5579

    Google Scholar 

  10. Unfortunately, the reactivity of HCCo2CrCp(CO)8 with bma could not be investigated due to the instability and facile decomposition of the chromium cluster

  11. Nestle MO, Hallgren JE, Seyferth D (1980) Inorg Synth 20:226

    Article  Google Scholar 

  12. (a) Beurich H, Blumhofer R, Vahrenkamp H (1982) Chem Ber 115:2409 (b) Blumhofer R, Fischer K, Vahrenkamp H (1986) Chem Be 119:194 (c) Jensen S, Robinson BH, Simpson J (1983) J Chem Soc Chem Commun 1081

  13. Fenske D, Becher HJ (1975) Chem Ber 119:2115

    Article  Google Scholar 

  14. Shriver DF (1969) The manipulation of air-sensitive compounds. McGraw-Hill, New York

    Google Scholar 

  15. SAINT Version 6.02, Bruker Advanced Analytical X-ray Systems, Inc. Copyright 1997–1999

  16. SHELXTL Version 5.1, Bruker Advanced Analytical X-ray Systems, Inc. Copyright 1998

  17. PLATON -A Multipurpose Crystallographic Tool (2001) Utrecht University, Utrecht, The Netherlands, Spek, AL

  18. Avey A, Schut DM, Weakley TJR, Tyler DR (1993) Inorg Chem 32:233

    Article  CAS  Google Scholar 

  19. (a) Watson WH, Chen T, Richmond MG (2004) J Chem Crystallogr 34:797 (b) Shen H, Wang JC, Bott SG, Richmond MG (1997) J Chem Crystallog 27:649

    Google Scholar 

  20. (a) Blumhofer R, Fischer K, Vahrenkamp H (1986) Chem Ber 119:194 (b) Bradford MR, Connelly NG, Harrison NC (1989) Organometallics 8:1829 (c) Sutin KA, Li L, Frampton CS, Sayer BG, McGlinchey MJ (1991) Organometallics 10:2362 (d) Jacobsen EN, Bergman RG (1985) J Am Chem Soc 107:2023 (e) Bruce MI, Halet J-F, Kahlal S, Low PJ, Skelton BW, White AH (1999) J Organomet Chem 578:155 (f) Zhang W-Q, Zhu, B-H, Hu B, Zhang Y-H, Zhao Q-Y; Yin Y-Q, Sun J (2004) J Organoomet Chem 689:714

  21. (a) Colbran SB, Robinson BH, Simpson (1986) J Acta Crystallogr C42:972 (b) Worth GH, Robinson BH, Simpson J (1990) J Organomet Chem 387:337 (c) Wu H-P, Yin Y-Q, Huang X-Y (1997) Inorg Chim Acta 255:167 (d) Watson WH, Poola B, Liu J, Richmond MG (2007) J Chem Crystallogr 37:349

  22. (a) Fogg DE, MacLaughlin SA, Kwek K, Cherkas AA, Taylor NJ, Carty AJ (1988) J Organomet Chem 352:C17 (b) Etienne M, Mathieu R, Lugan N (1993) Organometallics 12:140 (c) Chung M-C, Sakurai A, Akita M, Moro-Oka Y (1999) Organoometallics 18:4684 (d) Han L-M, Suo Q-L, Wang Y-B, Ye J-H, Zhu N, Leng X-B, Sun J (2005) Polyhedron 24:759

  23. For standard carbon-carbon single and double bond distances, see: Weast RC (ed) (1975) Handbook of chemistry and physics, 56th edn. CRC Press, Cleveland, OH

  24. For structural differences between the neutral bma-substituted fac-BrRe(CO)3(bma) compound and the corresponding bma-based radical anion, see: Yang K, Bott SG, Richmond MG (1995) Organometallics 14:2387

  25. (a) Seyferth D, Hallgren JE (1973) J Organomet Chem 49:C41 (b) Seyferth D, Rudie CN, Merola JS (1978) J Organomet Chem 162:89 (c) Strickland DS, Wilson SR, Shapley JR (1988) Organometallics 7:1674

  26. Mingos DMP, Wales DJ (1990) Introduction to cluster chemistry. Prentice-Hall, Englewood Cliffs, NJ

    Google Scholar 

  27. For comparable structural data on related Co2W clusters, see: (a) Chetcuti MJ, Chetcuti PAM, Jeffery JC, Mills RM, Mitrprachachon P, Pickering SJ, Stone, FGA (1982) J Chem Soc Dalton Trans 699 (b) Zhang J, Chen X-N, Yin Y-Q, Wang W-L, Huang X-Y (1999) J Organomet Chem 582:252 (c) Richter F, Vahrenkamp H (1982) Chem Ber 115:3224 (d) Roland E, Bernhardt W, Vahrenkamp H (1986) Chem Ber 119:2566 (e) Shiu Y-T, Madhushaw RJ, Li W-T, Lin Y-C, Lee G-H, Peng S-M, Liao F-L, Wang S-L, Liu R-S (1999) J Am Chem Soc 121:4066 (f) Jeffery JC, Lawerence-Smith JG (1985) J Organomet Chem 280:C34

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Texas Christian University, Fort Worth, TX, 76129, USA

    Weiqiang Zhang & William H. Watson

  2. Department of Chemistry, University of North Texas, Denton, TX, 76203, USA

    Michael G. Richmond

Authors
  1. Weiqiang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. William H. Watson
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Michael G. Richmond
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to William H. Watson or Michael G. Richmond.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, W., Watson, W.H. & Richmond, M.G. Diphosphine Substitution and Carbyne Ligand Transfer in the Reaction of 2,3-Bis(diphenylphosphino)maleic Anhydride (bma) with the Methylidyne-capped Clusters HCCo2MCp(CO)8 (where M=Mo, W): Synthesis and X-ray Diffraction Structures of the Vinylidene-bridged Clusters Co2MCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)]. J Chem Crystallogr 38, 437–445 (2008). https://doi.org/10.1007/s10870-008-9339-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10870-008-9339-5

Keywords

Search

Navigation