Synthesis and Reactivity of Group 12 β-Diketiminate Coordination Complexes

Abstract

<p>The variable β-diketiminate ligand poses as a suitable chemical environment to explore unknown reactivity and functionality of metal centres. Variants on the β-diketiminate ligand can provide appropriate steric and electronic stabilization to synthesize a range of β-diketiminate group 12 metal complexes. This project aimed to explore various β-diketiminate ligands as appropriate ancillary ligands to derivatise group 12 element complexes and investigate their reactivity. A β-diketiminato-mercury(II) chloride, [o-C₆H₄{C(CH₃)=N-2,6- iPr₂C₆H₃}{NH(2,6- iPr₂C₆H₃)}]HgCl, was synthesized by addition of [o-C₆H₄{C(CH₃)=N-2,6- iPr₂C₆H₃}{NH(2,6- iPr₂C₆H₃)}]Li to mercury dichloride. Attempts to derivatise the β-diketiminato-mercury(II) chloride using salt metathesis reactions were unsuccessful with only β-diketiminate ligand degradation products being observed in the ¹H NMR. A β-diketiminato-cadmium chloride, [CH{(CH₃)CN-2,6-iPr₂C₆H₃}₂]CdCl, was derivatized to a β-diketiminato-cadmium phosphanide, [CH{(CH₃)CN-2,6-iPr₂C₆H₃}₂]Cd P(C₆H₁₁)₂, via a lithium dicyclohexyl phosphanide and a novel β-diketiminato-cadmium hydride, [CH{(CH₃)CN-2,6-iPr₂C₆H₃}₂]CdH, via Super Hydride. Initial reactivity studies of the novel cadmium hydride with various carbodiimides yielded a β-diketiminato-homonuclear cadmium-cadmium dimer, [CH{(CH₃)CN-2,6-iPr₂C₆H₃}₂Cd]₂, which formed via catalytic reduction of the cadmium hydride. Attempts to synthesize an amidinate insertion product via a salt metathesis reaction or a ligand exchange reaction proved unsuccessful but a novel cadmium amidinate, [{CH(N-C₆H₁₁)₂}₂{CH(N-C₆H₁₁)(N(H)-C₆H₁₁)}Cd], was synthesized from addition of dicyclohexyl formamidine to bis-hexamethyldisilazane cadmium. A β-diketiminato-zinc(II) bromide, [o-C₆H₄{C(CH₃)=N-2,6- iPr₂C₆H₃}{NH(2,6- iPr₂C₆H₃)}]ZnBr, was synthesized by addition of [o-C₆H₄{C(CH₃)=N-2,6- iPr₂C₆H₃}{NH(2,6- iPr₂C₆H₃)}]Li to zinc dibromide. The β-diketiminato-zinc(II) bromide was derivatized to a variety of complexes (including amides and phosphanides) by a salt metathesis reaction. Chalcogen addition reactions were performed from [o-C₆H₄{C(CH₃)=N-2,6-iPr₂C₆H₃}{NH(2,6-iPr₂C₆H₃)}ZnP(C₆H₁₁)₂] to produce double addition products from sulfur, selenium and tellurium. Chalcogen addition reactions from [o-C₆H₄{C(CH₃)=N-2,6-iPr₂C₆H₃}{NH(2,6-iPr₂C₆H₃)}ZnP(C₆H₅)₂] produced a double addition product for selenium and a β-diketiminato-zinc(II) tellunoite bridged dimer, [o-C₆H₄{C(CH₃)=N-2,6-iPr₂C₆H₃}{NH(2,6-iPr₂C₆H₃)}Zn]Te, from tellurium. A total of 14 compounds were characterized via X-ray diffraction. Photoluminescence studies of the β-diketiminato-zinc(II) compounds were conducted where it was proposed that an electron transfer from the lone pair on the hetero-atom influenced the quantum yield and fluorescence intensities.</p>