Comparison of the coordination geometries of Zn(II) and Cd(II) ions in complexes with water, methanol and bulky aryloxysilanethiolate ligands. (5th September 2016)

• Record Type: Journal Article
• Authors: Jabłońska, Agnieszka; Bender, Johannes; Gudat, Dietrich; Ponikiewski, Łukasz; Dołęga, Anna
• Is Part Of: Polyhedron. Volume 115(2016)
• Page Start: 219
• Page End: 227
• Publication Date: 2016-09-05
• Subjects: Zinc -- Cadmium -- Aqua complex -- Methanol complex -- Silanethiolate complex; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2016.05.022
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Zinc and cadmium silanethiolates with methanol/water co-ligands were prepared and characterized by means of infrared spectroscopy, 1 H, 13 C and 113 Cd NMR spectroscopy, and single-crystal X-ray diffraction. Facile exchange of methanol to water within zinc complex was observed similar to the process undergoing in the active site of alcohol dehydrogenase. Abstract: Zinc and cadmium complexes containing silanethiolate anions and methanol or water were synthesized and characterized by X-ray diffraction, FT-IR and NMR spectroscopy, and DFT calculations. The Zn/Cd complexes1 and2 exhibit the same composition but different coordination spheres of the metal ions, [Cd{SSi(OAr)3 }2 (CH3 OH)]·CH3 OH (1 ) versus [Zn{SSi(OAr)3 }2 (CH3 OH)2 ] (2 ) where Ar = 2, 6-diisopropylphenyl. Contrary to zinc, the cadmium ion utilizes very weak donors to complete its coordination sphere; it forms contacts to phenyl rings of the silanethiolate ligand. Two zinc analogs of the general formula [Zn{SSi(OAr)3 }2 (L)2 ] where L = CH3 OH (2 ) or H2 O (3 ) are compared. In3, methanol is replaced by water even at low concentration of water in the reaction mixture. The exchange is accompanied by the reorganization of the hydrophobic environment of the water/methanol ligand in the complex. A tetranuclear zinc complex [Zn4 (CH3 OH)4 {SSi(OAr)3 }4 (CH3 COO)4 ]4 featuring an unusual unsupported [Zn4 (CH3 COO)4 ] 4+ core was also obtained and characterized.