Synthesis and reactions of substituted zirconocene and hafnocene dimethyls and the corresponding dihydrides

Couturier, Sarah; Gautheron, B.

doi:10.1016/s0022-328x(00)94033-6

Cited by 54 publications

(15 citation statements)

References 6 publications

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“…Carbonyl compounds, such as aldehydes [103,179], (thio)ketones [31,94,[180][181][182][183], carboxylic acids, and esters [183,184] with 1 are reduced to alcohols after hydrolysis [5], except in sterically hindered cases (see Section 8.5) [185,186]. Carbonyl compounds, such as aldehydes [103,179], (thio)ketones [31,94,[180][181][182][183], carboxylic acids, and esters [183,184] with 1 are reduced to alcohols after hydrolysis [5], except in sterically hindered cases (see Section 8.5) [185,186].…”

Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

“…Hydrozirconation of nitriles RC≡N with 1 led to the formation of aldimido [RCH=NZrCp 2 Cl] derivatives [183,[188][189][190][191]. Erker and coworkers reported the first X-ray structure analysis of these complexes, which shows a nearly linear Zr-N=CHPh unit indicating substantial Zr-N π character.…”

Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

“…to afford an η 2 -formaldehydo-type complex [(Cp 2 ZrCl)] 2 (µ-CH 2 O) [200][201][202]. Carbon dioxide [183,202] is reduced to formaldehyde with 1 (2 equiv.). Carbon dioxide [183,202] is reduced to formaldehyde with 1 (2 equiv.).…”

Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

“…As described in the previous section for unsaturated functional groups, Schwartz's reagent (1) and most zirconocene(IV) hydrides readily deprotonate acidic moieties [183,218]. Dienols with 2 equiv.…”

Section: Relative Reactivity Of C≡c and C=c Versus Carbonyl Functionsmentioning

confidence: 99%

“…Dienols with 2 equiv. Alkyl, aryl, silyl [85,112,183,210] and THP [17,153,211,219] ethers are stable under hydrozirconation conditions; side products were observed only with the trimethylsilyl group [220,221]. Alcohols can also be easily converted to ethers.…”

Section: Relative Reactivity Of C≡c and C=c Versus Carbonyl Functionsmentioning

confidence: 99%

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Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

Section: Hydrozirconation Across Heteropolar Multiple Bondsmentioning

confidence: 99%

Section: Relative Reactivity Of C≡c and C=c Versus Carbonyl Functionsmentioning

confidence: 99%

Section: Relative Reactivity Of C≡c and C=c Versus Carbonyl Functionsmentioning

confidence: 99%

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Hydrogenation with Early Transition Metal, Lanthanide and Actinide Complexes

Copéret¹

2006

The Handbook of Homogeneous Hydrogenation

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Christophe Copéret IntroductionHomogeneous hydrogenation catalysts have been mainly based on late transition-metal complexes since the discovery of Wilkinson's catalyst, [(Ph 3 P) 3 RhCl] [1]. Nonetheless, some of the first homogeneous catalysts to emerge were based on early transition metals. In fact, soon after the discovery of metallocene complexes [2,3], which were rapidly exploited as the soluble equivalent of Ziegler-Natta olefin polymerization catalysts [4], these systems were introduced as homogeneous hydrogenation catalysts [5][6][7][8][9][10][11]. Other Ziegler-Natta-type olefin polymerization catalysts, [L n MX n /M'R] {M = Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Ni, Pd, Ru; X = Cl, OR; M' = Al or Li, R = H, Et, Bu or iBu} were also investigated, and the results obtained showed that all metals could indeed activate H 2 and hydrogenate olefins. This pioneering chemistry most likely formed the basis for the discovery of most homogeneous catalyzed processes known to date, and has led to the development of well-defined systems and to the success of molecular organometallic chemistry and homogeneous catalysis [12,13].In hydrogenation, early transition-metal catalysts are mainly based on metallocene complexes, and particularly the Group IV metallocenes. Nonetheless, Group III, lanthanide and even actinide complexes as well as later metals (Groups V-VII) have also been used. The active species can be stabilized by other bulky ligands such as those derived from 2,6-disubstituted phenols (aryloxy) or silica (siloxy) (vide infra). Moreover, the catalytic activity of these systems is not limited to the hydrogenation of alkenes, but can be used for the hydrogenation of aromatics, alkynes and imines. These systems have also been developed very successfully into their enantioselective versions.This chapter will provide an overview of the development and use of early transition-metal complexes in hydrogenation, and in consequence has been divided into several sections. Section 6.2 will focus on the mechanistic differences in the hydrogenation reaction between early and late transition metals. The following three sections will describe the various systems based on Group IV (Sec-111 The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier 112 Scheme 6.1 Elementary steps for the hydrogenation of olefins with d 0 transition-metal complexes. 6.3 Group IV Metal Hydrogenation Catalysts 113 Scheme 6.2 r-Bond metathesis transition state. 6 Hydrogenation with Early Transition Metal, Lanthanide and Actinide Complexes 116 Scheme 6.5 First enantioselective hydrogenation by a Group IV metallocene catalysts.

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Zirconocenes

and¹,

Montchamp²

1998

Metallocenes

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Synthesis and reactions of substituted zirconocene and hafnocene dimethyls and the corresponding dihydrides

Cited by 54 publications

References 6 publications

Hydrozirconation

Hydrozirconation

Hydrogenation with Early Transition Metal, Lanthanide and Actinide Complexes

Zirconocenes

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