Skip to main content
Log in

Investigation of the volatile carboxylates of some platinum metals in the gaseous phase by electron-impact mass spectrometry

  • Published:
Theoretical and Experimental Chemistry Aims and scope

Abstract

The mass spectra of the compounds Rh2 (RCOO)4[R=C(CH3)3 (I), CH(CH3)2 (II), CF3 (III)], Pd3(RCOO)6 [R=C(CH3)3 (IV), CH(CH3)2 (V), CF3 (VI)], Os2(RCOO)4Cl2 [R=C(CH3)3 (VII)], and Ru2(RCOO)4 [R=C(CH3)3 (VIII)] have been investigated. It has been shown that in the gaseous state compounds I–III, VII, and VIII have a dimeric structure, while compounds IV–VI have a trimeric structure. The mass spectra of compounds I–VIII show peaks of the molecular ions [M]+; and the fragmentation of the molecular ions takes place mainly with the elimination of the RCOO groups. Rearrangements with the elimination of F2O have been discovered for compounds III and VI, and rearrangements with the elimination of O=C--OH have been discovered for IV and V. The migration of a fluorine atom to the metal in compound III and its absence in compound V have been explained in the framework of the principle of hard and soft acids and bases. A scheme for the fragmentation of [M]+. under the action of electron impact has been proposed.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

Literature cited

  1. A. Dobson and S. D. Robinson, “Carboxylato complexes of the platinum group metals,” Platinum Metals Rev., 20, No. 1, 56–63 (1976).

    Google Scholar 

  2. M. A. Porai-Koshits, “Crystal chemistry and stereochemistry of carboxylates. Stereochemical classification of monobasic carboxylates and factors determing the structural function of carboxylato ligands in complexes of transition metals,” in: Results of Science and Technology. Crystal Chemistry [in Russian], Vol. 15, VINITI, Moscow (1981), pp. 3–129.

    Google Scholar 

  3. E. B. Boyar and S. D. Robinson, “Rhodium(II) carboxylates,” Coord. Chem. Rev., 50, No. 1/2, 109–208 (1983).

    Google Scholar 

  4. N. V. Gérbéléu and K. M. Indrichan, Mass Spectrometry of Coordination Compounds [in Russian], Shtiintsa, Kishinev (1984).

    Google Scholar 

  5. N. V. Gérbéléu, G. A. Popovich, K. M. Indrichan, and G. A. Timko, “Mass-spectrometric investigation of binuclear chromium(II) carboxylates,” Zh. Neorg. Khim., 28, No. 12, 3035–3038 (1983).

    Google Scholar 

  6. G. A. Popovich, K. M. Indrichan, and G. A. Timko, “Composition and structure of manganes (II), cobalt(II), and nickel(II) pivalates in the gaseous phase,” in: Fourth All-Union Conference on the Chemistry of Coordination Compounds of Manganese, Cobalt, and Nickel. Abstracts of Reports, Tbilisi, November 28–30, 1983 [in Russian], Tbilisi (1983), p. 113.

  7. N. V. Gérbéléu, G. A. Popovich, and K. M. Indrichan, “Investigation of the structure of scandium, yttrium, and lanthanide pivalates in the gaseous phase by mass spectrometry,” in: Eighth All-Union Conference on Physical and Mathematical Methods in Coordination Chemistry. Abstracts of Reports, Kishinev, October 31-November 3, 1983 [in Russian], Shtiintsa, Kishinev (1983), pp. 176–177.

    Google Scholar 

  8. N. V. Gérbéléu, K. M. Indrichan, G. A. Popovich, and G. A. Timko, “Mass spectrometry of homo- and heteronculear chromium(III) and iron(III) pivalates,” in: Fifth All-Union Conference on the Analytical Chemistry of Organic Compounds. Abstracts of Reports, Moscow, December 11–14, 1984 [in Russian], Nauka, Moscow (1984), pp. 216–217.

    Google Scholar 

  9. K. M. Indrichan, N. V. Gérbéléu, and G. A. Popovich, “Mass-spectric investigation of lead(II) carboxylates,” Zh. Neorg. Jhim., 29, No. 6, 1450–1453 (1984).

    Google Scholar 

  10. G. A. Timko and K. M. Indrichan, “Investigation of rhodium(II) and palladium(II) pivalates in the gaseous phase by an electron-impact method,” in: Conference of Young Scientists of the Academy of Sciences of the Moldavian SSR. Youth, Science, and Industry. Abstracts of Reports, Kishinev, December 18–19, 1984 [in Russian], Shtiintsa, Kishinev (1984), pp. 148–149.

    Google Scholar 

  11. N. V. Gérbéléu, G. A. Popovich, and K. M. Indrichan, “Mass spectra of mercury(II) carboxylates,” Zh. Neorg. Khim., 29, No. 11, 2959–2961 (1984).

    Google Scholar 

  12. J. Kitchens and J. L. Bear, “The thermal decomposition of some rhodium(II) carboxylate complexes,” Thermochim. Acta, 1, No. 4, 537–544 (1970).

    Google Scholar 

  13. F. A. Cotton and T. R. Felthouse, “Structural studies of three tetrakis(carboxylato)dirhodium(II) adducts in which carboxylate groups and axial ligands are varied,” Inorg. Chem., 19, No. 2, 323–328 (1980).

    Google Scholar 

  14. F. A. Cotton (editor), Inorganic Syntheses, Vol. 13, Mcgraw-Hill, New York (1972).

    Google Scholar 

  15. T. A. Stephenson, S. M. Morehouse, A. R. Powell et al., “Carboxylates of palladium, platinum, and rhodium, and their adducts,” J. Chem. Soc., No. 6, 3623 (1965).

    Google Scholar 

  16. T. Behling, G. Wilkinson, T. A. Stephenson, et al., “Synthesis and reactions of osmium (III) chloro carboxylates. X-ray crystal structure of tetra(μ-n-butyrato)-dichlorodiosmium(III) (Ox-Os),” J. Chem. Soc Dalton Trans., No. 9, 2109–2117 (1983).

    Google Scholar 

  17. R. C. Pearson, “Hard and soft acids and bases,” J. Am. Chem. Soc., 85, No. 2, 3533–3539 (1963).

    Google Scholar 

  18. K. B. Yatsimirskii, “Acid-base and donor-acceptor properties of ions and molecules,” Teor. Éksp. Khim., 6, No. 4, 462–468 (1970).

    Google Scholar 

  19. M. L. Morris and R. D. Koob, “Mass spectra of rhenium(III) and rutheium(III) complexes of 2,4-pentanedione, 1, 1, 1,-trifluoro-2,4-pentanedione, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione,” Inorg. Chem., 22, No. 24, 3502–3506 (1984).

    Google Scholar 

  20. M. Das, “Mass spectra of scadium(III) and yttrium(III) complexes of trifluoromethyl-β-diketones,” Inorg. Chim. Acta, 83, No. 1, L1-L3 (1984).

    Google Scholar 

  21. A. S. Skapski and M. L. Smart, “The crystal structure of trimeric palladium(II) acetate,” J. Chem. Soc. Chem. Commun., No. 11, 658–659 (1970).

    Google Scholar 

  22. F. A. Cotton and S. Han, “The structure of trinuclear palladium(II) acetate as crystallized from benzene,” Rev. Chim. Minerale, 20, No. 4/5, 496–503 (1983).

    Google Scholar 

  23. N. V. Gérbéléu, K. M. Indirichan, G. A. Timko, and G. A. Popovich, “Composition and structure of pivalates of divalent 3d elements in the gaseous phase,” Dokl. Akad. Nauk SSSR, 280, No. 2, 377–380 (1985).

    Google Scholar 

  24. F. A. Cotton, A. R. Chakravarty, D. A. Tocher, and T. A. Stephenson, “Structural and mass spectral studies of some multiply bonded diosmium tetracarboxylate compounds,” Inorg. Chim. Acta, 87, No. 2, 115–119 (1984).

    Google Scholar 

  25. A. J. Lindsay, R. P. Tooze, M. Motevalli, et al., “The synthesis and structure of tetra-μ-acetatodiruthenium(II,II)-bis(tetrahydrofuran),” J. Chem. Soc. Chem. Commun., 20, 1383–1384 (1984).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 22, No. 3, pp. 322–330, May–June, 1986.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gérbéléu, N.V., Timko, G.A., Indrichan, K.M. et al. Investigation of the volatile carboxylates of some platinum metals in the gaseous phase by electron-impact mass spectrometry. Theor Exp Chem 22, 304–312 (1986). https://doi.org/10.1007/BF00521157

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00521157

Keywords

Navigation