Synthesis and Structure of [Cu(Hapn)]NO3]NO3, [Cu(Hapn)(H2O)2]SiF6, [Cu(Hapn)(H2O)BF4]BF4 · H2O and [Cu(Hapn)(NH2SO3)2] π-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile).

Mykhailo Luk'Yanov,Evgeny Goreshnik,Marian Mys’Kiv,Vasyl Kinzhybalo

doi:10.17344/acsi.2016.3116

Abstract

Four copper(I) π-complexes: [Cu(Hapn)NO3]NO3 (1), [Cu(Hapn)(H2O)2]SiF6 (2), [Cu(Hapn)(H2O)BF4]BF4·H2O (3) and [Cu(Hapn)(NH2SO3)2] (4) were prepared using alternating-current electrochemical technique, starting from alcohol solutions of 3-(prop-2-en-1-ylamino)propanenitrile (apn) titrated with appropriate acid and copper(II) salts (Cu(NO3)2 · 3H2O, CuSiF6 · 4H2O, Cu(BF4)2 · 6H2O or Cu(NH2SO3)2 · xH2O, respectively). Obtained compounds were characterized by single-crystal X-ray diffraction and partially by IR spectroscopy. In the structures of complexes 1, 2 and 4 Cu(I) cation possesses a tetrahedral environment formed by the C=C bond of one organic cation Hapn, the N atom of cyano group from another Hapn moiety, and two O atoms (from NO3- anions in 1, from H2O molecules in 2) or N atoms (NH2SO3- anions in 4). In compound 3 strongly pronounced trigonal-pyramidal coordination environment of Cu(I) is formed by a mid-point of C=C-bond of one Hapn cation, nitrogen atom (of cyano group) of another Hapn unit, O atom of H2O molecule in the basal plane, and F atom of BF4- anion at the apical position.

Highlights

For almost two centuries the attention of scientists within different branches has been paid to aminonitriles, ranging from α-aminonitriles discovered by A
It has been noticed that atoms of Cl or Br compete for space in coordination polyhedron with allyl groups and cyano group in the halide complexes of Cu(I) with diallylaminopropanenitrile.[16,17]
Colourless needle-like crystals of complex 4 appeared from a methanol solution (4 mL) of Cu(NH2SO3)2 · xH2O (4.1 mmol) and the apn (4.1 mmol) previously titrated with water solution of 50% NH2SO3H to pH 6.5 under conditions of the alternating-current electrochemical technique (U = 0.6 V, Iinit = 0.4 mA) during 7 days

Summary

Introduction

For almost two centuries the attention of scientists within different branches has been paid to aminonitriles, ranging from α-aminonitriles discovered by A. The coordination behaviour of aminonitriles in the complexation reactions with Cu(I) salts can be characterized on the basis of only several related,[13,14] or closely related,[15] compounds, though the matter under discussion is still relevant. Depending on the status (cation or molecular) of 3-(prop-2-en-1-ylamino)propanenitrile the number of active groups for coordination changes, which, in turn, influences the composition of coordination polyhedron of the Cu ion Cationic form of apn provides these groups the same chance to be coordinated with the metal atom: C=C ≥ C≡N > Hal. In order to study a coordination ability of C=C-bond or C≡N-group to the copper atom, the compounds with ionic copper salts have been studied. We have undertaken the synthesis and crystal structure determination of copper(I)-π-complexes with 3-(prop-2-en-1-ylamino)propanenitrile

Experimental

Results and Discussion

Conclusions