Synthesis and Reactivity of Group 12 β-Diketiminate Coordination Complexes

<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>

Synthesis and Reactivity of Group 12 β-Diketiminate Coordination Complexes

<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>

Cleavage of C-O and C-H bonds in ethers by a genuine Si=O bond

An isolable three-coordinate dialkylsilanone without a substantial electronic stabilization reacts with several ethers resulting in the cleavage of the C-O or C-H and C-O bonds in ether which have not...

Electronic stabilization by occupational disorder in the ternary bismuthide Li3–x–y In x Bi (x ≃ 0.14, y ≃ 0.29)

A ternary derivative of Li3Bi with the composition Li3–x–y In x Bi (x ≃ 0.14, y ≃ 0.29) was produced by a mixed In+Bi flux approach. The crystal structure adopts the space group Fd\overline{3}m (No. 227), with a = 13.337 (4) Å, and can be viewed as a 2 × 2 × 2 superstructure of the parent Li3Bi phase, resulting from a partial ordering of Li and In in the tetrahedral voids of the Bi fcc packing. In addition to the Li/In substitutional disorder, partial occupation of some Li sites is observed. The Li deficiency develops to reduce the total electron count in the system, counteracting thereby the electron doping introduced by the In substitution. First-principles calculations confirm the electronic rationale of the observed disorder.

Nickel(II)-Methyl Complexes Adopting Idealized Seesaw Geometries

We report four-coordinate nickel(II)-methyl complexes of tris-carbene borate ligands which adopt rare seesaw geometries. Experimental and computational results suggest the structural distortion from threefold symmetry results from a combination of electronic stabilization of the singlet state, strong field donors, and constrained angles from the chelating ligand.

Nickel(II)-Methyl Complexes Adopting Idealized Seesaw Geometries

We report four-coordinate nickel(II)-methyl complexes of tris-carbene borate ligands which adopt rare seesaw geometries. Experimental and computational results suggest the structural distortion from threefold symmetry results from a combination of electronic stabilization of the singlet state, strong field donors, and constrained angles from the chelating ligand.