ISSN:
0044-2313
Keywords:
Tetrathiooxalate
;
Trithiooxalate
;
1,1-Dithiooxalate
;
Photolytic Reactions
;
Moleculer Structure
;
Copper(I) Complexes
;
Extended Hückel Calculations
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Photolytic Reactions of Binuclear Thiooxalate Complexes - Crystal and Moleculer Structure of Hydrogensulfidopyridinebis(triphenylphosphane)copper(I)Solutions of the binuclear, thiooxalato bridged complexes with capping triphenylphosphane ligands are lightsensitive and decompose mainly with decomposition of the bridging thiooxalate. From μ-1,1-Dithiooxalatobis[bis(triphenylphosphane)copper(I)], [{(Ph3P)2Cu}2(i-dto)], in dichloromethane the binuclear copper(I) complex μ-dichlorotris(triphenylphosphane)dicopper(I), [(Ph3P)2CuCl2Cu(Ph3P)], with the total lost of the bridging thiooxalato ligand is formed. μ-Trithiooxalato-bis-[bis(triphenylphosphane)copper(I)], [{(Ph3P)2Cu}2(trto)], decomposes in pyridine with the formation of hydrogensulfidopyridinebis(triphenylphosphane)copper(I), [(Ph3P)2(py)CuSH]. This complex crystallizes in the triclinic space group P1, with the unit cell parameters a = 9,488(2) Å, b = 10,472(3) Å, c = 19,351(3) Å, α = 85,03(2)°, β = 86,99(2)° and γ = 68,36(2)°. Contrast ngly, the bridging thiooxalate ligand in the corresponding binuclear tetrathiooxalate complex, [{(Ph3P)2Cu}2(tto)], obviously remains unchanged. The proposed reaction pathways are supported by the results of Extended Hückel Calculations.
Notes:
Die Lösungen thiooxalatverbrückter Zweikernkomplexe mit terminalen Triphenylphosphanliganden sind lichtempfindlich und zersetzen sich überwiegend unter Zerfall des Thiooxalato-Brückenliganden. μ-1,1-Dithiooxala-to-bis[bis(triphenylphosphan)-kupfer(I)], [{(Ph3P)2Cu}2(i-dto)], bildet in Dichlormethan unter Verlust des Thiooxalato-Brückenliganden den chloroverbrückten Kupfer(I)-Zweikernkomplex μ-Dichlorotris(triphenylphosphan)dikupfer(I), [(Ph3P)2CuCl2Cu(Ph3P)]. μ-Trithiooxalato-bis[bis(triphenyl-phosphan)kupfer(I)], [{(Ph3P)2Cu}2(trto)], zersetzt sich in Pyridin unter Bildung von Hydrogensulfidopyridin-bis(triphenylphosphan)kupfer(I), [(Ph3P)2 (py)CuSH]. Der gebildete Komplex kristallisiert in der triklinen Raumgrupe P1, mit dem Elementarzellenparametern a = 9,488(2) Å, b = 10,472(3) Å, c = 19,351 (3) Å, α = 85,03(2)°, β = 86,99(2)° und γ = 68,36(2)°. Im Unterschied dazu bleibt beim entsprechenden Tetrathiooxalat-Zweikernkomplex, [{(Ph3P)2Cu}2(tto)], der Thiooxalato-Brückenligand offensichtlich erhalten. Die angenommenen Reaktionswege konnten durch quantenchemische Berechnungen (EHT) gestützt werden.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19976230121
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