ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Tetrathiosquarate, C4S42-, a Versatile Ligand in Metal Complexes, II1)Tetrathiosquarate acts as bridging bis(chelate) ligand in the complexes (PPh3)2MC4S4M-(PPh3)2 (M = Cu, Ag, Rh) (1a, b, d), Ph3PAuC4S4AuPPh3 (1c), [(Et3P)2PtC4S4Pt(PEt3)2]2+ (Cl-)2 (1e), [Cl2PdC4S4PdCl2]2- (AsPh4+)2 (1f), [(Ph3P)2PtC4S4Pt(PPh3)2]2- (AsPh4+)2 (1g), and in Me2AuC4S4AuMe2 (1h), as monochelate in (Ph2PCH2CH2PPh2)NiC4S4 (2) [C4S4Ni(py)2 C4S4]2- (AsPh4+)2·2 Pyridin (3) and [C4S4ZnC4S4]2- (AsPh4+)2. On the basis of the bond lengths obtained by an X-ray structure analysis the ligand in 3 can be formulated as dithioxocyclobutenedithiolate. Polymeric complexes presumably with chain structure of approximate composition (M2C4S4)n (M1 = Cu, Ag, Au) and (MC4S4)n (MII = Cu, Zn, Cd, Hg, Fe, Co, Ni, Pd, Pt, Sn, Pb) precipitate from aqueous solutions of K2C4S4 and metal salts. Oligomeric complexes [C4S4MC4S4MC4S4]2- (AsPh4+)2 (7) (M = Mn, Fe, Co, Ni) and [Cun(C4S4)n+1]2- (AsPh4+)2 (9) (n = 3, 11) have been obtained from nonaqueous solutions using (AsPh4)2C4S4. [C4S4GePh3]-K+ (10), {C4S4[Co(biacetyl dioximate)2 pyridine]2} (11), {C4S4[Co(biacetyl dioximate)2PPh3]4}2+ (Cl-)2 (12), and [Mo(C4S4)Mo]4- (AsPh4+)4 (13) are complexes with C4S42- as one-, two- or fourfold monodentate ligand, respectively.
Notes:
Tetrathioquadratat tritt in den Komplexen (Ph3P)2MC4S4M(PPh3)2 (M = Cu, Ag, Rh) (1a, b, d), Ph3Ph3PAuC4S4AuPPh3 (1c), [(Et3P)2PtC4S4Pt(PEt3)2]2+ (Cl-)2 (1e), [Cl2PdC4S4PdCl2]2- (AsPh4+)2 (1f), [(Ph3P)2PtC4S4Pt(PPh3)2]2- (AsPh4+)2 (1g) sowie in Me2AuC4S4AuMe2 (1h) als verbrückender Bis(chelat)-Ligand auf. Als Monochelat-Ligand wird C4S42- in (Ph2PCH2-CH2PPh2)NiC4S4 (2), [C4S4Ni(py)2C4S4]2- (AsPh4+)2·2 Pyridin (3) und [C4S4ZnC4S4]2- (AsPh4+)2 (4) gefunden. Nach den durch Röntgenstrukturanalyse ermittelten Abständen läßt sich der Ligand in 3 als Dithioxocyclobutendithiolat formulieren. Polymere Verbindungen der ungefähren Zusammensetzung (M2C4S4)n (MI = Cu, Ag, Au) und (MC4S4)n (MII = Cu, Zn, Cd, Hg, Fe, Co, Ni, Pd, Pt, Sn, Pb) mit vermutlicher Kettenstruktur entstehen aus K2C4S4 und den Metallsalzen in wäßriger Lösung. Oligomere Komplexe definierter Zusammensetzung [C4S4MC4S4MC4S4]2- (AsPh4+)2 (7) (M = Mn, Fe, Co, Ni) und [Cun-(C4S4)n+1]2- (AsPh4+)2 (9) (n = 3, 11) wurden mit (AsPh4)2C4S4 in nicht-wäßrigem Medium erhalten. (C4S4GePh3)-K+ (10), {C4S4[Co(biacetyldioximat)2Pyridin]2} (11), {C4S4[Co(biacetyldioximat)2PPh3]4}2+ (Cl-)2 (12) und [Mo(C4S4)4Mo]4- (AsPh4+)4 (13) sind Komplexe mit C4S42- als ein-, zwei- bzw. vierfach einzähliger Ligand.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19861190412
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