Summary
A simple low-voltage electrochemical technique was used to obtain crystalline anionic halo-salts of cobalt. Complexes of the type [R3PH]2[CoX4] (R=n-Bu, Ph or 4-totyl; X=Cl or Br) and [H2P-P][CoX4][P-P = bis(diphenylphosphino)methane or bis(diphenylphosphino)ethane; X=Cl or Br] were synthesized by the one-step electrochemical oxidation of cobalt in an acetonitrile-hydrohalic acid solution of the neutral tertiary or ditertiary phosphine. I.r. absorption and n.m.r. spectra (1H and31P) provided diagnostic criteria for confirming the presence of the phosphonium cation rather than the ligated phosphine.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
G. Brauer (Ed),Handbook of Preparative Inorganic Chemistry, Vol. 2, 2nd Edit., Academic Press Inc. N.Y., 1965, p. 1341.
J. J. Habeeb and D. G. Tuck,Chem. Comm., 808 (1975).
F. F. Said and D. G. Tuck,Can. J. Chem.,59, 62 (1981).
J. J. Habeeb, L. Neilson and D. G. Tuck,Synth. React. Inorg. Metal-org. Chem.,6, 105 (1976).
J. J. Habeeb, F. F., Said and D. G. Tuck,Can. J. Chem.,55, 3882 (1975).
J. J. Habeeb and D. G. Tuck,J. Chem. Soc., Dalton Trans., 866 (1976).
M. J. Taylor and D. G. Tuck,Inorg. Synth.,22, 135 (1983).
M. Khan, C. Oldham, M. J. Taylor and D. G. Tuck,Inorg. Nucl. Chem. Lett.,16, 469 (1980).
A. T. Casey and A. M. Vecchio,Transition Met. Chem.,11, 366 (1986).
A. T. Casey and A. M. Vecchio, submitted for publication inJ. Coord. Chem., (1987).
A. T. Casey and A. M. Vecchio,Inorg. Chim. Acta, (1987) in press.
A. I. Vogel,Textbook of Quantitative Inorganic Analyses, 3rd Edit., Longmans, Green and Co. Ltd., London, 1968.
N. F. Curtis,J. Chem. Soc., 3147 (1961).
J. W. Geary,Coord. Chem. Rev.,7, 81 (1971).
D. G. Tuck,J. Chem. Ed.,59, 420 (1982).
R. L. Carlin,Transition Metal Chemistry, Vol. 3, Marcel Dekker, Inc., N.Y., 1965.
A. B. P. Lever,Inorganic Electronic Spectroscopy, Elsevier, N.Y., 1968
D. Sutton,Electronic Spectra of Transition Metal Complexes, McGraw-Hill, London, 1968
R. S. Drago,Physical Methods in Chemistry, W. B. Saunders Co., Philadelphia, 1977.
F. A. Cotton, D. M. L. Goodgame and M. Goodgame,J. Am. Chem. Soc.,83, 4691 (1961).
W. van Erk and C. Haas,Phys. Status Solidii,71b, 537 (1975).
R. Colton and J. H. Canterford,Halides of the First Row Transition Metals, Wiley International, N.Y., 1969.
J. C. Sheldon and S. Y. Tyree Jr.,J. Am. Chem. Soc.,80, 2117 (1958).
D. E. Corbridge,Topics in Phosphorus Chemistry,6, 235 (1967).
R. M. Silverstein, C. G. Bassler and T. C. Morrill,Spectrometric Identification of Organic Compounds, 3rd Edit., John Wiley and Sons, N.Y., 1974.
G. Witschard and C. E. Griffin,Spectrochim. Acta.,19, 1905 (1963).
L. C. Thomas,The Identification of Functional Groups in Organophosphorus Compounds, Academic Press, London, 1974, p. 113.
R. A. Jones and M. A. Talmet,Aust. J. Chem.,15, 903 (1965).
F. G. Geol and R. G. Montemayor,Inorg. Chem.,16, 2183 (1977).
J. F. Brazier, D. Houalla, M. Loenig and R. Wolf,Topics in Phosphorus Chem.,8, (1976).
C. Pouchert,The Aldrich Library of NMR Spectra Ed. H., Aldrich Chemical Co. Inc., USA, 1983.
J. R. Van Wazer, H. H. Crutchfield, C. H. Dungan, J. H. Letcher and V. Mark,Topics in Phosphorus Chemistry,5, (1967).
S. O. Grim and W. McFarlane,Can. J. Chem.,46, 2071 (1968).
H. Finegold,Ann. N.Y. Acad. Sci.,70, 875 (1958).
J. Emsley and D. Hall,The Chemistry of Phosphorus, Wiley N.Y., 1976.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Casey, A.T., Vecchio, A.M. The electrochemical synthesis of anionic cobalt halide complexes with several quaternary and diquaternary phosphorus cations. Transition Met Chem 12, 295–298 (1987). https://doi.org/10.1007/BF01024016
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01024016