Combined experimental and theoretical studies of dithiocarbamate complexes of yttrium, lanthanum and bismuth

• Main Author: Gowda, Vasantha
• Format: Others
• Language: English
• Published: Luleå tekniska universitet, Kemiteknik 2014
• Subjects: Physical Chemistry; Fysikalisk kemi
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:ltu:diva-25701; http://nbn-resolving.de/urn:isbn:978-91-7583-055-1; http://nbn-resolving.de/urn:isbn:978-91-7583-056-8

Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metalseparation science, and have potential use as chemotherapeutic, pesticides, and as additives tolubricants. A highly versatile dialkyldithiocarbamate (R2NCS2–) ligand can form stablecomplexes with all the transition elements and also the majority of main group, lanthanide andactinide elements. Here we present structural investigations of the molecular and electronicstructures of dialkyldithiocarbamate complexes with yttrium(III), lanthanum(III), andbismuth(III) of molecular formula [Y{S2CN(C2H5)2}3PHEN], [La{S2CN(C2H5)2}3PHEN], and[Bi2{S2CN-n(C4H9)2}6] (where PHEN=1,10-Phenanthroline) . The experimental solid-state 13Cand 15N cross polarization magic-angle-spinning (CP-MAS) NMR results are reported for allthese three complexes. We also report new single-crystal X-ray structures of heterolepticyttrium, lanthanum, and homoleptic bismuth dialkyldithiocarbamate complexes. Thecomparative analysis of powder XRD patterns and solid-state 13C and 15N CP-MAS spectra ofpolycrystalline yttrium(III) and lanthanum(III) diethyldithiocarbamato-phenanthrolinecomplexes shows the presence of significant structural differences. The diethyldithiocarbamatophenanthrolinecomplex of yttrium has a very similar structural type to a previously reported Xraydiffraction structure for [Nd{S2CN(C2H5)2}3PHEN] whereas, the crystal structure of[La{S2CN(C2H5)2}3PHEN] is considerably more complex. Our NMR and single-crystal X-raydiffraction results suggested polymorphism for bismuth di-n-butyldithiocarbamate complex.Finally, the experimental NMR results are complemented by chemical shifts obtained usingquantum chemical methods and verified the spectral assignments. Overall, our workdemonstrates how different experimental and theoretical methods can be combined that canafford insights into the solid-state structure and bonding environments of metal complexes. === Godkänd; 2014; 20141024 (vasgow); Nedanstående person kommer att hålla licentiatseminarium för avläggande av teknologie licentiatexamen. Namn: Vasantha Gowda Ämne: Gränsytors kemi/Chemistry of Interfaces Uppsats: Combined Experimental and Theoretical Studies on Dithiocarbamate Complexes of Yttrium, Lanthanum, and Bismuth Examinator: Professor Oleg Antzutkin, Institutionen för samhällsbyggnad och naturresurser, Luleå tekniska universitet Diskutant: Huvudforskare John V. Hanna, Department of Physics, University of Warwick, Storbritannien Tid: Fredag den 28 november 2014 kl 10.15 Plats: C305, Luleå tekniska universitet