The synthesis and properties of diarylgoldzinc chlorides, diphenylgoldcadmium chloride, and diphenylgoldmercury chloride

GRAAF, P. W. J. DE; Koning, A. J. De; Boersma, J.; Kerk, G.J.M. van der

doi:10.1016/s0022-328x(00)90859-3

Cited by 14 publications

(5 citation statements)

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“…The important role of transient zinc alkyl adducts of transition metal alkyl cations in polymerization catalysis was mentioned above in the Introduction. Neutral μ-aryl-bridged Au/Zn bi- and trimetallic compounds have been reported. , Reaction of ZnMe 2 with RuHCl(PPh 3 ) 3 gave an ill-defined Ru−Zn 2 −Ru heterotetrametallic species, and that with IrMe(PMe 3 ) 4 gave fac -IrMe 2 (ZnMe)(PMe 3 ) 3 . Bimetallic species involving Ni(μ-Me)Zn interactions have been proposed as intermediates in certain Ni-catalyzed coupling reactions involving organozincs …”

Section: Resultsmentioning

confidence: 99%

AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

et al. 2006

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A combined experimental and DFT study of the reactions of the titanium imido methyl cation [Ti(NtBu)(Me3[9]aneN3)Me]+ (4+) with AlMe3 and ZnMe2 is described. Reaction of 4+ with AlMe3 gave [Ti(NtBu)(Me3[9]aneN3)(mu-Me)2AlMe2]+ (7+), the first structurally characterized AlMe3 adduct of a transition metal alkyl cation and a model for the presumed resting state in MAO-activated olefin polymerizations. Reaction of 4+ with ZnMe2 also gave a methyl-bridged heterobinuclear species, namely [Ti(mu-NtBu)(Me3[9]aneN3)(mu-Me)2ZnMe]+ (8+), the first directly observed ZnMe2 adduct of a transition metal alkyl cation. At room temperature, all three metal-bound methyls of 8+ underwent rapid exchange with those of free ZnMe2, whereas at 233 K only the terminal Zn-Me group exchanged significantly. Addition of AlMe3 to 8+ quantitatively formed 7+ and ZnMe2. Reaction of 4+ with Cp2ZrMe2 gave [Ti(NtBu){Me2(mu-CH2)[9]aneN3}(mu-CH2)ZrCp2]+ (10+) via a highly selective double C-H bond activation reaction in which both alkyl groups of Cp2ZrMe2 were lost. DFT calculations on models of 7+ confirmed the approximately square-based pyramidal geometries for the bridging methyl groups. Calculations on 8+ found that the formation of the Ti(mu-Me)2Zn moiety is assisted by an Nimide-->Zn dative bond. DFT calculations for the sterically less encumbered methyl cation [Ti(NMe)(H3[9]aneN3)Me]+ found strong thermodynamic preferences for adducts featuring Nimide-->M (M = Al or Zn) interactions. This offers insight into recently observed structure-productivity trends in MAO-activated imido-based polymerization catalysts. Calculations on the metallocenium adducts [Cp2Ti(mu-Me)2AlMe2]+ and [Cp2Ti(mu-Me)2ZnMe]+ are described, each showing alpha-agostic interactions for the bridging methyl groups. For these systems and the imido ones, the coordination of AlMe3 to the corresponding monomethyl cation is ca. 30 kJ mol-1 more favorable than for ZnMe2.

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Section: Resultsmentioning

confidence: 99%

AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

et al. 2006

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“…Zinc alkyls are generally monomeric and stable hetero bimetallic alkyl-bridged complexes involving zinc are very much rarer compared to aluminum. Only an ill-defined methyl-bridged ruthenium−zinc complex, and a phenyl-bridged gold−zinc complex have been reported . To date, we have not succeeded in isolating an iron−zinc species.…”

Section: Discussionmentioning

confidence: 99%

“…Only an ill-defined methyl-bridged ruthenium-zinc complex, 100 and a phenyl-bridged gold-zinc complex have been reported. 101 To date, we have not succeeded in isolating an ironzinc species. However, the self-exchange of alkyl groups in dialkyl zinc species is common, 102 and diphenyl zinc is dimeric in the solid state.…”

Section: Discussionmentioning

confidence: 99%

Iron Catalyzed Polyethylene Chain Growth on Zinc: A Study of the Factors Delineating Chain TransferversusCatalyzed Chain Growth in Zinc and Related Metal Alkyl Systems

et al. 2004

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The bis(imino)pyridine iron complex, [[2,6-(MeC=N-2,6-iPr2C6H3)2C5H)N]FeCl2] (1), in combination with MAO and ZnEt2 (> 500 equiv.), is shown to catalyze polyethylene chain growth on zinc. The catalyzed chain growth process is characterized by an exceptionally fast and reversible exchange of the growing polymer chains between the iron and zinc centers. Upon hydrolysis of the resultant ZnR2 product, a Poisson distribution of linear alkanes is obtained; linear alpha-olefins with a Poisson distribution can be generated via a nickel-catalyzed displacement reaction. Other dialkylzinc reagents such as ZnMe2 and ZniPr2 also show catalyzed chain growth; in the case of ZnMe2 a slight broadening of the product distribution is observed. The products obtained from Zn(CH2Ph)2 show evidence for chain transfer but not catalyzed chain growth, whereas ZnPh2 shows no evidence for chain transfer. The Group 13 metal alkyl reagents AlR3 (R = Me, Et, octyl, IBu) and GaR3 (R = Et, nBu) act as highly efficient chain transfer agents, whereas GaMe3 exhibits behavior close to catalyzed chain growth. LinBu, MgnBu2 and BEt3 result in very low activity catalyst systems. SnMe4 and PbEt4 give active catalysts, but with very little chain transfer to Sn or Pb. The remarkably efficient iron catalyzed chain growth reaction for ZnEt2 compared to other metal alkyls can be rationalized on the basis of: (1) relatively low steric hindrance around the zinc center, (2) their monomeric nature in solution, (3) the relatively weak Zn-C bond, and (4) a reasonably close match in Zn-C and Fe-C bond strengths.

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“…After 15 h the solvent was evaporated and the residue extracted with dichloromethane (3 x 6 em3). The resulting solution was concentrated (1 cm3) and diethyl ether (10 cm3) slowly added to precipitate complex (2) which was recrystallized from dichloromethane-diethyl ether ( 11) 2 130 (11) 1441 (11) (3 Y 5 crn3) for (6)]. The suspension was filtered off and the resulting solution concentrated (1 cm3) and n-hexane (10 cm3) added to precipitate the corresponding complex which was recrystallized from diethyl ether-n-hexane (1 : 5 ) [for (4 j (6)] or acetone-n-hexane (1 : 5) [for (3)].…”

Section: 7 1)mentioning

confidence: 99%

Bis[2-(phenylazo)phenyl-C¹N′]gold(III) complexes. Crystal and molecular structure of bis[2-(phenylazo)phenyl-C¹N′]gold(III) tetrachloroaurate

Vicente¹,

Chicote²,

Bermúadez³

et al. 1984

J. Chem. Soc., Dalton Trans.

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The synthesis and properties of diarylgoldzinc chlorides, diphenylgoldcadmium chloride, and diphenylgoldmercury chloride

Cited by 14 publications

References 9 publications

AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

Iron Catalyzed Polyethylene Chain Growth on Zinc: A Study of the Factors Delineating Chain TransferversusCatalyzed Chain Growth in Zinc and Related Metal Alkyl Systems

Bis[2-(phenylazo)phenyl-C¹N′]gold(III) complexes. Crystal and molecular structure of bis[2-(phenylazo)phenyl-C¹N′]gold(III) tetrachloroaurate

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The synthesis and properties of diarylgoldzinc chlorides, diphenylgoldcadmium chloride, and diphenylgoldmercury chloride

Cited by 14 publications

References 9 publications

AlMe3and ZnMe2Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

AlMe3and ZnMe2Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

Iron Catalyzed Polyethylene Chain Growth on Zinc: A Study of the Factors Delineating Chain TransferversusCatalyzed Chain Growth in Zinc and Related Metal Alkyl Systems

Bis[2-(phenylazo)phenyl-C1N′]gold(III) complexes. Crystal and molecular structure of bis[2-(phenylazo)phenyl-C1N′]gold(III) tetrachloroaurate

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AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

AlMe₃and ZnMe₂Adducts of a Titanium Imido Methyl Cation: A Combined Crystallographic, Spectroscopic, and DFT Study

Bis[2-(phenylazo)phenyl-C¹N′]gold(III) complexes. Crystal and molecular structure of bis[2-(phenylazo)phenyl-C¹N′]gold(III) tetrachloroaurate