Bonding studies on zinc, cadmium, and mercury alkyls and amides, Zn(CH2EMe3)2 (E  C or Si) and M[N(SiMe3)2]2 (M  Zn, Cd, or Hg). Heats of Hydrolysis, standard heats of formation, and ZnC and MN (M  Zn, Cd, or Hg) bond energy terms

Gümrükçüoğlu, İsmail Erdem; Jeffery, John C.; Läppert, Michael F.; Pedley, J. B.; Audesh, K.

doi:10.1016/0022-328x(88)89062-4

Cited by 30 publications

(6 citation statements)

References 4 publications

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“…* For reference, we are aware of few comparisons between Zn–X and Cd–X BDEs, but note that the Zn–N BDE of Zn[N(SiMe 3 ) 2 ] 2 is 15.6 kcal mol −1 stronger than the corresponding Cd–N bond in Cd[N(SiMe 3 ) 2 ] 2 , 32 while the Zn–C BDE of Me 2 Zn is 8.7 kcal mol −1 stronger than the corresponding Cd–C bond in Me 2 Cd. 30 Thus, if the difference in Zn–Me and Cd–Me BDEs of [Tm Bu t ]MMe were to be of a comparable value to the above Zn–X and Cd–X BDEs, the Zn–[Tm Bu t ] interaction would be predicted to be stronger than the Cd–[Tm Bu t ] interaction.…”

Section: Resultsmentioning

confidence: 99%

Exchange of alkyl and tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligands between zinc, cadmium and mercury

Kreider-Mueller

Quinlivan

Rong

et al. 2015

Journal of Organometallic Chemistry

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The tris(2-mercaptoimidazolyl)hydroborato ligand, [TmBut], has been used to investigate the exchange of alkyl and sulfur donor ligands between the Group 12 metals, Zn, Cd and Hg. For example, [TmBut]2Zn reacts with Me2Zn to yield [TmBut]ZnMe, while [TmBut]CdMe is obtained readily upon reaction of [TmBut]2Cd with Me2Cd. Ligand exchange is also observed between different metal centers. For example, [TmBut]CdMe reacts with Me2Zn to afford [TmBut]ZnMe and Me2Cd. Likewise, [TmBut]HgMe reacts with Me2Zn to afford [TmBut]ZnMe and Me2Hg. However, whereas the [TmBut] ligand transfers from mercury to zinc in the methyl system, [TmBut]HgMe/Me2Zn, transfer of the [TmBut] ligand from zinc to mercury is observed upon treatment of [TmBut]2Zn with HgI2 to afford [TmBut]HgI and [TmBut]ZnI. These observations demonstrate that the phenomenological preference for the [TmBut] ligand to bind one metal rather than another is strongly influenced by the nature of the co-ligands.

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Section: Resultsmentioning

confidence: 99%

Exchange of alkyl and tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligands between zinc, cadmium and mercury

Kreider-Mueller

Quinlivan

Rong

et al. 2015

Journal of Organometallic Chemistry

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“…20 Since the Cd-C bond dissociation energy D 0 for dimethylcadmium is only 281 kJ mol 21 21 it is very likely that the first reaction step after the injection of the precursor into TOPO at T~350 uC is the rupture of the Cd-C bonds. The precursors we used as substitutes for Me 2 Cd all have Cd-C bonds, some with additional ligands that coordinate via nitrogen atoms (the Cd-N bond is weaker than the Cd-C bond, e.g., 144 kJ mol 21 in Cd[(NSiMe 3 ) 2 ] 22 ). The weakness of the Cd-C bonds leads to the expected independence of the reaction on the choice of precursor and demonstrates that it is possible to avoid the use of the dangerous and toxic dimethylcadmium without loss in quality.…”

Section: Transmission Electron Microscopymentioning

confidence: 99%

Synthesis of CdSe nanoparticles using various organometallic cadmium precursors

2001

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Investigations into replacing Me 2 Cd as a common precursor for the synthesis of CdSe nanoparticles by pyrolysis in a hot coordinating solvent have proven that more stable, less volatile or even crystalline organometallic cadmium compounds can be used instead of Me 2 Cd. Dineopentylcadmium, bis(3-diethylaminopropyl)cadmium and (2,2'-bipyridine)dimethylcadmium have been used successfully as cadmium sources for the preparation of tri-n-octylphosphine oxide (TOPO)-capped CdSe nanoparticles. The resulting nanocrystallites have been characterized by UV-VIS and IR spectroscopy, photoluminescence spectroscopy (PL), mass spectrometry and transmission electron microscopy (TEM). They consist of separated, well defined spherical particles and show a small size distribution as well as a characterisitic blue shift due to quantum confinement in their optical spectra. The replacement of Me 2 Cd by less dangerous organometallic precursors thus results in nanocrystallites that show no reduction in quality when compared to the standard method.

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“…The mean Zn-C bond dissociation energies (D) (see Bond Dissociation Energy) have been determined by calorimetric studies for some of the compounds listed in Table 1. 34 In the particular case of Me 2 Zn, the first-and second-bond dissociation energies have also been calculated 35 …”

Section: Properties Of Diorganozinc Compoundsmentioning

confidence: 99%

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Gr��vy¹

2005

Encyclopedia of Inorganic Chemistry

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Since the discovery of the first organozinc compounds by Sir Edward Frankland in 1849, the organometallic chemistry of zinc made remarkable advances and organozinc species have become essential tools for organic chemists. During the past decade, numerous new and modified procedures for the preparation of the title compounds have been published, rendering their synthesis easier, faster, and less expensive and giving higher yields. The coordination chemistry of organozinc derivatives has been subject of further interest and various intra‐ and intermolecular complexes with different donor ligands have been structurally characterized by X‐ray crystallography and spectroscopic methods. The accumulation of molecular structures, physicochemical studies, and computational calculations has led to a better understanding of the organozinc chemistry, and consequently to the design of new derivatives for specific applications. Even if the development of areas like the chemistry of organozinc anions and cations is still in its early stage, these compounds, which exhibit properties different than those of the parent organometallic species, appear to have promising applications in synthesis and catalytic reactions. During the past ten years, the chemistry of organo‐ gem ‐dizincio derivatives has also been the subject of much interest and progress. These reagents can form two carbon–carbon bonds in a one‐pot reaction and with high stereoselectivity. They became key reagents for organic chemists who want to combine multiple transformations in one operation. The importance of organometallic compounds of zinc can be seen in the growing number of their applications in synthesis. They are used in many reactions such as substitutions, additions to carbonyl compounds and unsaturated systems, cyclopropanations, and polymerizations. Furthermore, as a result of their low reactivity, they tolerate a wide variety of functionalities and perform most of the transformations with high regio‐ and enantioselectivity. After spending more than half a century in the shade of Grignard and organolithium reagents, organozinc reagents are becoming more and more important in modern chemistry.

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Bonding studies on zinc, cadmium, and mercury alkyls and amides, Zn(CH2EMe3)2 (E  C or Si) and M[N(SiMe3)2]2 (M  Zn, Cd, or Hg). Heats of Hydrolysis, standard heats of formation, and ZnC and MN (M  Zn, Cd, or Hg) bond energy terms

Cited by 30 publications

References 4 publications

Exchange of alkyl and tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligands between zinc, cadmium and mercury

Exchange of alkyl and tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligands between zinc, cadmium and mercury

Synthesis of CdSe nanoparticles using various organometallic cadmium precursors

Zinc: Organometallic ChemistryBased in part on the article Zinc: Organometallic Chemistry by Gerard Parkin which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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