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CO Substitution and Cluster-Ligand Reductive Coupling in the Reaction of 2,3-Bis(diphenylphosphino)maleic Anhydride (bma) with the Mixed-metal Clusters PhCCo2MCp(CO)8 (where M = Cr, W): Synthesis and X-ray Diffraction Structures of the Phosphido-bridged Clusters Co2MCp(CO)5[μ2,η2,η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ-PPh2)

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Abstract

The ligand substitution behavior of the mixed-metal tetrahedrane clusters PhCCo2MCp(CO)8 [where M = Cr (1), W (3)] with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) has been examined, and the phosphido-bridged clusters Co2MCp(CO)5[μ2,η2,η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ-PPh2) [where M = Cr (2), W (4)] have been confirmed as the principal reaction products. Both 2 and 4 have been isolated and characterized in solution by IR and 31P NMR spectroscopies, and the molecular structures established by X-ray diffraction analyses. Clusters 2 and 4 each contain 48e− and exhibit triangular Co2M cores that are bridged by a phosphido moiety across the M–Co bond and face-capped by a six-electron μ2,η2,η1-C(Ph)C=C(PPh2)C(O)OC(O) ligand. The reactivity of clusters 1 and 3 with bma is contrasted to the corresponding molybdenum clusters PhCCo2MoCp(CO)8 and PhCCo2Mo(indenyl)(CO)8 previously investigated by our groups.

Graphical Abstract

CO Substitution and Cluster-Ligand Reductive Coupling in the Reaction of 2,3-bis(diphenylphosphino)maleic Anhydride (bma) with the Mixed-metal Clusters PhCCo 2 MCp(CO) 8 (where M = Cr, W): Synthesis and X-ray Diffraction Structures of the Phosphido-bridged Clusters Co 2 MCp(CO) 5 [μ 2 ,η 2 ,η 1 -C(Ph)C=C(PPh 2 )C(O)OC(O)](μ-PPh 2 )

Weiqiang Zhang, William H. Watson, Michael G. Richmond

Thermolysis of the mixed-metal clusters PhCCo2MCp(CO)8 [where M = Cr (1), W (3)] with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) affords the phosphido-bridged clusters Co2MCp(CO)5[μ2,η2,η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ-PPh2) [where M = Cr (2), W (4)]. The new clusters have been isolated and characterized in solution by IR and 31P NMR spectroscopies and their solid-state structures established by X-ray crystallography. The reactivity of clusters 1 and 3 with bma is discussed relative to the corresponding molybdenum clusters PhCCo2MoCp(CO)8 and PhCCo2Mo(indenyl)(CO)8.

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References

  1. (a) Watson WH, Wu G, Richmond MG. Organometallics 2005, 24:5431; 2006, 25:931; (b) Watson WH, Kandala S, Richmond MG (2007) J Organomet Chem 692:968, 1648

  2. (a) Bott SG, Yang K, Talafuse KA, Richmond MG (2003) Organometallics 22:1383; (b) Bott SG, Shen H, Senter RA, Richmond MG (2003) Organometallics 22:1953; (c) Bott SG, Shen H, Richmond MG (2004) J Organomet Chem 689:3426; (d) Bott SG, Yang K, Richmond MG (2005) J Organomet Chem 690:3067; (e) Bott SG, Yang K, Richmond MG (2006) J Organomet Chem 691:20; (f) Watson WH, Bodige SG, Ejsmont K, Liu J, Richmond MG (2006) J Organomet Chem 691:3609

  3. (a) Yang K, Smith JM, Bott SG, Richmond MG (1993) Organometallics 12:4779; (b) Bott SG, Shen H, Richmond MG (2001) Struct Chem 12:225

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

    Article  CAS  Google Scholar 

  5. Watson WH, Poola B, Richmond MG (2006) J Organomet Chem 691:5579

    Google Scholar 

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

    Article  Google Scholar 

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

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

    Article  Google Scholar 

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

    Google Scholar 

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

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

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

  13. Bott SG, Yang K, Huang S-H, Richmond MG (2004) J Chem Crystallogr 34:883

    Article  CAS  Google Scholar 

  14. (a) Yang K, Bott SG, Richmond MG (1995) Organometallics 14:2387; (b) Yang K, Martin JA, Bott SG, Richmond MG (1996) Organometallics 15:2227

  15. While no mechanistic implication is made here, dissociative CO loss from the molybdenum center in the putative cluster PhCCo2MoCp(CO)6(bma) would be accord with the rates of dissociative CO loss in mononuclear Group 6 compounds. See: Collman JP, Hegedus LS, Norton JR, Finke RG (1987) Principles and applications of organotransition metal chemistry, University Science Books, Mill Valley

  16. (a) Garrou PE (1981) Chem Rev 81:229; (b) Carty AJ, MacLaughlin SA, Nucciarone D (1987) In: Verkade JG, Quin LD (eds) Phosphorus-31 NMR spectroscopy in stereochemical analysis: organic and metal complexes, chapter 16. VCH Publishers, New York

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

    Google Scholar 

  18. (a) Eremenko IL, Pasynskii AA, Gasanov GS, Orazsakhatov B, Struchkov YT, Shklover VE (1984) J Organomet Chem 275:71; (b) Eremenko IL, Pasynskii AA, Orazsakhatov B, Shestakov AF, Gasanov GS, Katugin AS, Struchkov YT, Shklover VE (1988) J Organomet Chem 338:369; (c) Song L-C, Cheng H-W, Hu Q-M, Wang Z (2004) J Organomet Chem 689:139; (d) Wadepohl H, Galm W, Pritzkow H (1989) Angew Chem Int Ed 28:345; (e) Watson WH, Ejsmont K, Liu J, Richmond MG (2006) J Chem Crystallogr 36:823

  19. (a) Sanchez-Nieves J, Sterenberg BT, Udachin KA, Carty AJ (2004) J Cluster Sci 15:151; (b) Henkel G, Tremel W, Krebs B (1983) Angew Chem Int Ed 22:318; (c) Burt JC, Boese R, Schmid G (1978) J Chem Soc Dalton Trans 1387; (d) Conole G, Davies JE, King JD, Mays MJ, McPartlin M, Powell HR, Raithby PR (1999) J Organomet Chem 585:141

  20. Weast RC (ed) (1975) Handbook of chemistry and physics, 56th edn. CRC Press, Cleveland

    Google Scholar 

  21. (a) Curtis MD, Han KR, Butler WM (1980) Inorg Chem 19:2096. (b) Here the asymmetry parameter, α, is formally defined as: α = (d2 − d1)/d1; where d2 and d1 represent the longer and shorter M–CO distances, respectively

  22. (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

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Acknowledgment

Financial support from the Robert A. Welch Foundation (Grants P-0074-WHW and B-1093-MGR) is appreciated.

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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

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  1. Weiqiang Zhang
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  2. William H. Watson
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  3. Michael G. Richmond
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Correspondence to William H. Watson or Michael G. Richmond.

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Zhang, W., Watson, W.H. & Richmond, M.G. CO Substitution and Cluster-Ligand Reductive Coupling in the Reaction of 2,3-Bis(diphenylphosphino)maleic Anhydride (bma) with the Mixed-metal Clusters PhCCo2MCp(CO)8 (where M = Cr, W): Synthesis and X-ray Diffraction Structures of the Phosphido-bridged Clusters Co2MCp(CO)5[μ2,η2,η1-C(Ph)C=C(PPh2)C(O)OC(O)](μ-PPh2). J Chem Crystallogr 38, 9–15 (2008). https://doi.org/10.1007/s10870-007-9261-2

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