Structurally well-characterized new multinuclear Cu(ii) and Zn(ii) clusters: X-ray crystallography, theoretical studies, and applications in catalysis. (20th October 2016)

• Record Type: Journal Article
• Authors: Ansari, Istikhar A.; Sama, Farasha; Raizada, Mukul; Shahid, M.; Ahmad, Musheer; Siddiqi, Zafar A.
• Is Part Of: New journal of chemistry. Volume 40:Number 11(2016:Nov.)
• Page Start: 9840
• Page End: 9852
• Publication Date: 2016-10-20
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c6nj02150f
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : Cu3 and Zn2 clusters with aminotriethanolate and benzoate bridging are characterized as new catalysts for hydrocarboxylation of alkanes and cycloalkanes. Abstract : Two new trinuclear Cu(ii ) and dinuclear Zn(ii ) clusters are crystallized out by reacting the metal salts with the triethanolamine (H3 tea) ligand in the presence of benzoic acid (Hba). The complexes are characterized by elemental, thermal, magnetic, spectral (FTIR, UV-Visible, EPR, and photoluminescence) and single crystal X-ray studies. Single crystal X-ray crystallography reveals the composition of the complexes to be [Cu3 (H2 tea)2 (ba)2 (NO3 )2 ] (1 ) and [Zn2 (H2 tea)(ba)3 ]H2 O (2 ). FTIR ascertains the binding modes of H2 tea −, ba − and NO3 − . Triethanolamine binds in both the complexes in the monoanionic (H2 tea − ) mode. ba − is present as an anchoring auxiliary to generate di- and trinuclear clusters. The Cu(ii ) ion is present as a distorted octahedral center in the Cu3 cluster (1 ), while the two Zn(ii ) ions in2 have been reported for the first time to possess distorted octahedral as well as tetrahedral geometry in the same molecule. The intriguing features of the non-covalent supramolecular interactions have been investigated and supported theoretically by using Hirshfeld surface analysis and ab initio methods. The solid state photoluminescence (PL) spectra of1 and2 disclose the luminescence property of the complexes. Due to the closed or nearly closed shell configuration (d 9 or d 10 ), the present complexes are screened for catalytic properties in the hydrocarboxylation of alkanes and cycloalkanes. The catalytic activity data are indicative of the potential catalytic properties of1 and2 .