Abstract
Crystallochemical treatment of the Nieuwland reaction is carried out on the basis of structural data obtained for crystalline acetylene complexes of the formulas NH4Cu8Cl9·4C2H2·1/2HCu2Cl3·H2O (I), NH4Cu3Cl4·C2H2 (II), KCu8Cl9·4C2H2·1/2HCu2Cl3·H2O (III), KCu3Cl4·C2H2 (IV), (NH4)2Cu3Cl5·4/9H2O·(xC2H2) with x=0 (Va), 1/9 (Vb), and 4/9 (Vc) and divinylacetylene (DVA) copper chloride compounds 2CuCl·DVA (VI) and 3CuCl·DVA (VII). Because of the π-coordination of a copper atom, the C≡C bond of the acetylene molecule is activated, as indicated by its significant (up to 1.32 Å) stretch (complexes I and II). The zeolite-like structure of complexes Va-Vc, which form in a catalytic solution, is realized as an infinite {[Cu108Cl168(H2O)16]60−}n anion with discrete [Cl(NH4)6]5+ cations inside. In this structure, only 16 Cu(1) atoms have a trigonal-pyramidal environment with the oxygen atom of the crystallization water located in the vertex (dCu−O=2.79 Å). Under the liquid-phase conditions of the Nieuwland reaction, these copper atoms are active centers stimulating the reaction to the subsequent acetylene oligomerization due to the π-interaction with the C2H2 molecule. The mutual arrangement of the catalytically active Cu(1) atoms in structure Va serves as a matrix for the synthesis of DVA, as shown by the structure of the 2CuCl·DVA adduct.
Similar content being viewed by others
References
J. A. Nieuwland, W. S. Calcott, and F. B. Downing,J. Am. Chem. Soc.,53, No. 11, 4197–4202 (1931).
L. G. Tsyurikh and A. A. Ginzburg,Zh. Obshch. Khim. 5, No. 10, 1468–1478 (1935).
O. N. Temkin, T. G. Sukhova, G. K. Shestakov, et al.,Kinet. Katal.,10, No. 5, 1004–1009 (1969).
A. L. Klebanskii, I. M. Dolgopolskii, and Z. F. Dobler,Dokl. Akad. Nauk SSSR,114, No. 2, 323–336 (1957).
I. M. Dolgopolskii and M. Kh. Blyumental,Zh. Obshch. Khim.,29, No. 7, 2512–2517 (1959).
O. A. Chaltykyan,Cuprocatalysis [in Russian], Aipetrat, Erevan (1963).
S. I. Osechkin, M. G. Myskiv, P. Yu. Zavalii and A. N. Sobolev,Metalloorg. Khim.,4, No. 5, 997–1003 (1991).
B. M. Mykhalichko, M. G. Myskiv, P. Yu. Zavalii, et al.,Koordinats. Khim.,17, No. 6, 827–832 (1991).
M. G. Myskiv, P. Yu. Zavalii, B. M. Mykhalichko, and V. S. Fundamenskii, ——ibid.,14, No. 12, 1619–1624 (1988).
M. Chavastelon,C. R. Acad. Sci. Paris 130, No. 26, 1764–1766 (1990).
O. N. Temkin, G. K. Shestakov, and Yu. A. Treger,Acetylene: Chemistry, Reaction Mechanisms, Technology [in Russian], Khimiya, Moscow (1991).
C. Brink and C. H. Macgillavari,Acta Crystallogr,2, 158–160 (1949).
M. G. Myskiv, S. I. Osechkin, P. Yu. Zavalii, and V. S. Fundamenskii,Koordinats. Khim.,14, No. 4, 524–529 (1988).
S. N. Bhakay-Tamhane, A. Sequeira, and R. Chidombaram,Struct. Rep.,B36, 2925–2929 (1980).
Additional information
I. Franko Lvov State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 5, pp. 120–132, September–October, 1994.
Translated by T. Yudanova
Rights and permissions
About this article
Cite this article
Myskiv, M.G., Mykhalichko, B.M. Nieuwland's cuprocatalytic reaction in terms of crystal chemical analysis. J Struct Chem 35, 677–687 (1994). https://doi.org/10.1007/BF02578338
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02578338