ISSN:
0044-2313
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis and Structure of Pentaazadienido Complexes of Copper(I) and Copper(II). Crystal Structures of [Cu(F—C6H4N5C6H4—F) (py)]2, [Cu(Cl—C6H4N5C6H4—Cl) (py)]2, [Cu(CH3O—C6H4N5C6H4—OCH3) (py)]2Cu(NH3)42+ reacts in conc. aqueous NH3 with RN2NHN2R to yield insoluble, brownish CuII pentaazadienido complexes Cu(RN5R)2 (R = p-F—C6H4, p-Cl—C6H4, p-MeO—C6H4). The dry compounds are explosiv. They decompose in hot THF or toluene under reduction of CuII to form the CuI complexes Cu(RN5R) from which upon addition of pyridine the dinuclear, red complexes [Cu(RN5R) (py)]2 (R = p-F—C6H4 (1), p-Cl—C6H4 (2) and p-MeO—C6H4 (3)) are obtained.1 crystallizes in two monoclinic modifications: I: P21/c; a = 1370.7(3), b = 1145,2(1), c = 2436.9(3) pm, β = 91.68(1)º, Z = 4, V = 3823.8 · 106 pm3, II: P21/n; a = 1448.2(3), b = 1102.2(1), c = 2276,8(3) pm, β = 102.55(1)º, Z = 4, V = 3547.5 · 106 pm3. 2 forms monoclinic crystals with the space group P21/c; a = 1095.6(6), b = 1820,2(6), c = 1007.5(3) pm, β = 114.12(3), Z = 2; 3 crystallizes monoclinic: P21/c; a = 1213.5(5), b = 1813.8(5), c = 990.0(3) pm, β = 116.76(2)º, Z = 2.The pentaazadienid ion functions in all complexes as bridging ligand with (N1)-η1, (N3)-η1 coordination, resulting in short Cu—Cu distances of 255.2 to 258.0 pm. The pyridine molecules are bound to the Cu atoms being in 1 in a cis and in 2 and 3 in trans arrangement with respect to the Cu—Cu axis.
Notes:
Cu(NH3)42+ reagiert in konz. wässerigem NH3 mit RN2NHN2R unter Bildung schwerlöslicher CuII-pentaazadienido-Komplexe Cu(RN5R)2 (R = p-F—C6H4, p-Cl—C6H4, p-MeO—C6H4). Die im trockenen Zustand explosiven Verbindungen zersetzen sich beim Erhitzen in THF oder Toluol unter Reduktion des Kupfers zu den CuI-Komplexen Cu(RN5R), aus denen mit Pyridin die zweikernigen, roten Komplexe [Cu(RN5R) (py)]2 (R = p-F—C6H4 (1), p-Cl—C6H4 (2) und p-MeO—C6H4 (3)) entstehen. 1 kristallisiert in zwei monoklinen Modifikationen. I: P21/c; a = 1370,7(3), b = 1145,2(1), c = 2436,9(3) pm, β = 91,68(1)º, Z = 4, V = 3823,8 · 106 pm3, II: P21/n; a = 1448,2(3), b = 1102,2(1), c = 2276,8(3) pm, β = 102,55(1)º, Z = 4, V = 3547,5 · 106 pm3. 2 bildet monokline Kristalle mit der Raumgruppe P21/c; a = 1095,6(6), b = 1820,2(6), c = 1007,5(3) pm, β = 114,12(3)º, Z = 2; 3 kristallisiert ebenfalls monoklin: P21/c; a = 1213,5(5), b = 1813,8(5), c = 990,0(3) pm, β = 116,76(2)º, Z = 2.Das Pentaazadienidion fungiert in allen Komplexen als Brückenligand mit (N1)-η1, (N3)-η1-Koordination, so daß kurze Cu—Cu-Abstände im Bereich von 255,2 bis 258,0 pm resultieren. Die Pyridinmoleküle sind an die Cu-Atome gebunden und in 1 bezüglich der Cu—Cu-Achse in cis- und in 2 und 3 in trans-Stellung angeordnet.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19895750122
