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Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I, II) Chlorides. Syntheses and Crystal Structures of [CuCl 2 ·2C 3 N 3 (OC 3 H 5 ) 3 ], [Cu 7 Cl 8 ·2C 3 N 3 (OC 3 H 5 ) 3 ], and [Cu 8 Cl 8 ·2C 3 N 3 (OC 3 H 5 ) 3 ]·2C 2 H 5 OH
Author(s) -
Goreshnik E. A.,
Ciunik L. Z.,
Gorelenko Yu. K.,
Mys'kiv M. G.
Publication year - 2004
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200400218
Subject(s) - copper , crystal structure , crystallography , valence (chemistry) , chemistry , electrochemistry , chloride , stereochemistry , electrode , organic chemistry
Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl 2 ·2C 3 N 3 (OC 3 H 5 ) 3 ] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu I, II π, σ‐complex of [Cu 7 Cl 8 ·2C 3 N 3 (OC 3 H 5 ) 3 ] ( II ). Final reduction produces [Cu 8 Cl 8 ·2C 3 N 3 (OC 3 H 5 ) 3 ]·2C 2 H 5 OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) Å 3 , Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) Å 3 , Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) Å 3 , Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl 2 ·2C 3 N 3 (OC 3 H 5 ) 3 ] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu 6 Cl 6 , whereas isolated Cu 6 Cl 6 (CuCl) 2 prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu II ‐atom through the N atom and to two Cu I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.