Related Experiment Video
Updated: Mar 28, 2026

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
Published on: June 8, 2022
Synthetic and reactivity studies of hetero-tri-anionic sodium zincates
Javier Francos1, Alan R Kennedy, Charles T O'Hara
1WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK. charlie.ohara@strath.ac.uk.
Abstract:
The synthesis and characterisation of several sodium zincate complexes are reported. The all-alkyl monomeric sodium zincate, (PMEDTA)·Na(μ-CH2SiMe3)Zn(t)Bu22, is prepared by combining equimolar quantities of (t)Bu2Zn, (n)BuNa and PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine)]. A similar approach was used to prepare and isolate the unusual dimeric zincate [(PMEDTA)·Na(μ-(n)Bu)Zn(t)Bu2]23. When an equimolar mixture of (n)BuNa, (t)Bu2Zn and TMP(H) (2,2,6,6-tetramethylpiperidine) is combined in hexane, the hetero-tri-leptic TMP(H)-solvated zincate (TMPH)Na(μ-TMP)(μ-(n)Bu)Zn(t)Bu 4 results. Complex 4 can also be prepared using a rational approach [i.e., utilising two molar equivalents of TMP(H)]. When TMEDA is reacted with an equimolar mixture of (n)BuNa, (t)Bu2Zn and TMP(H), the monomeric sodium zincate (TMEDA)Na(μ-TMP)(μ-(n)Bu)Zn(t)Bu 5 was obtained - this complex is structurally similar to the synthetically useful relation (TMEDA)·Na(μ-TMP)(μ-(t)Bu)Zn((t)Bu) 1. By changing the sodium reagent used in the synthesis of 5, it was possible to prepare (TMEDA)Na(μ-TMP)(μ-Me3SiCH2)Zn(t)Bu 6. By reacting 5 with cis-DMP(H) (cis-2,6-dimethylpiperidine), the zincate could thermodynamically function as an amide base, to give the transamination product (TMEDA)Na(μ-cis-DMP)(μ-(n)Bu)Zn(t)Bu 7, although no crystals could be grown. However, when HMDS(H) (1,1,1,3,3,3-hexamethyldisilazane) or PEA(H) [(+)-bis[(R)-1-phenylethyl]amine] is reacted with 5, crystalline (TMEDA)Na(μ-HMDS)(μ-(n)Bu)Zn(t)Bu 8 or (TMEDA)Na(μ-PEA)(μ-(n)Bu)Zn(t)Bu 9 is isolated respectively. With PNA(H) (N-phenylnaphthalen-1-amine) the reaction took a different course and resulted in the formation of the dimeric sodium amide complex [(TMEDA)Na(PNA)]210. When reacted with benzene, it appears that a TMEDA-free variant of 5 functions thermodynamically as an (n)Bu base to yield the previously reported (TMEDA)Na(μ-TMP)((t)Bu)Zn(μ-C6H4)Zn((t)Bu)(μ-TMP)Na(TMEDA) 11. Finally when reacted with TEMPO (2,2,6,6-tetramethylpiperidinyloxy), 5 undergoes a single electron transfer reaction to form (TMEDA)Na(μ-TMP)(μ-TEMPO)Zn(n)Bu 12.
More Related Videos
10:42Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
07:50Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Related Concept Videos
Diazonium Group Substitution: –OH and –H
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Ionic Crystal Structures
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Crystal Field Theory - Tetrahedral and Square Planar Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...