Yttrium‐Amidopyridinate Complexes: Synthesis and Characterization of Yttrium‐Alkyl and Yttrium‐Hydrido Derivatives

Luconi, Lapo; Lyubov, Dmitry M.; Bianchini, Claudio; Rossin, Andrea; Faggi, Cristina; Fukin, Georgy K.; Cherkasov, Anton V.; Shavyrin, A. S.; Giambastiani, Giuliano

doi:10.1002/ejic.200900934

Cited by 40 publications

(21 citation statements)

References 89 publications

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“…Interestingly, these complexes were active in ethylene polymerization; hence, a more detailed discussion is presented in Sect. 4 [29].…”

Section: Reactions Of Metal Complexes That Produce Pincer Complexesmentioning

confidence: 97%

“…Trifonov and Giambastiani et al studied amine-triggered alkane elimination from [29] in an effort to synthesize yttrium imido complexes [77]. Although reactions with equimolar quantities of 2,6-diisopropylaniline were proposed to proceed through a putative imido intermediate, only the resultant anilido or bis(anilido) products were observed (Scheme 37).…”

Section: Earth Metal Tetramethylaluminate Complexes Bearing Another [mentioning

confidence: 98%

“…A notable reduction in catalytic activity was observed when the metalated sp 2 carbon of the aryl substituent was replaced by an sp 3 hybridized carbon, 174. Under all conditions tested, the dinuclear hydride complexes 29, 30, and 176 were completely inactive [29].…”

Section: Other Polymerization Reactionsmentioning

confidence: 99%

See 2 more Smart Citations

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

Hänninen

Zamora

Hayes

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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The research field surrounding rare earth pincer complexes has reached a stage where a comprehensive review about the reactivity and catalytic behavior of these species is justified. In this contribution, we begin with a brief introduction on common strategies for the preparation of rare earth pincer complexes, continuing with a section devoted to the versatile reactivity observed for this class of compound. Thereafter, several types of compounds are discussed, including extremely reactive hydrides, cationic species, and intriguing scandium imido complexes. Finally, the last portion of this chapter sums up the hitherto reported catalytic studies, including discussions on ring-opening polymerization of cyclic esters, polymerization of olefins and hydroamination reactions, as well as several examples of more infrequently encountered catalytic processes.

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“…Interestingly, these complexes were active in ethylene polymerization; hence, a more detailed discussion is presented in Sect. 4 [29].…”

Section: Reactions Of Metal Complexes That Produce Pincer Complexesmentioning

confidence: 97%

Section: Earth Metal Tetramethylaluminate Complexes Bearing Another [mentioning

confidence: 98%

See 1 more Smart Citation

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

Hänninen

Zamora

Hayes

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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“…[22] Notably, no hydrogenolysis of the metalÀaryl or metalÀ benzyl bonds was observed, even with an excess of silane and longer reaction times. [22] Notably, no hydrogenolysis of the metalÀaryl or metalÀ benzyl bonds was observed, even with an excess of silane and longer reaction times.…”

Section: Bis(guanidinate)mentioning

confidence: 99%

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

et al. 2014

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Molecular hydrides of the rare-earth metals play an important role as homogeneous catalysts and as counterparts of solid-state interstitial hydrides. Structurally well-characterized non-metallocene-type hydride complexes allow the study of elementary reactions that occur at rare-earth-metal centers and of catalytic reactions involving bonds between rare-earth metals and hydrides. In addition to neutral hydrides, cationic derivatives have now become available.

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“…噻吩或苯并呋喃取代的胺基吡啶在烷烃消除反应中, 杂芳基 3-位同样发生分子内 sp 2 C-H 键活化反应 [209] . Figure 40 Intramolecular C-H activation of yttrium alkyl complex supported by bulky aminopyridinate ligand 通过盐消除 [206] 或烷烃消除反应都能顺利合成胺基吡啶稀土双烷基配合物, 其与硼盐反应生成的阳离子配合物是乙烯聚合的高活性催化剂 [210] . 胺基吡啶稀土双烷基配合物与 PhSiH 3 或 H 2 反应生成三核稀土单烷基多氢配合物, 该配合物与硼盐反应生成罕见的稀土多氢阳离子配合物 [211] .…”

Section: β-二亚胺稀土金属有机配合物 β-二亚胺是最为重要的双齿配体unclassified

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

Changtao¹,

Wang²,

Chen³

2014

Acta Chim. Sinica

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Rare-earth elements include scandium, yttrium and fifteen lanthanides. Since Wilkinson and Birmingham reported the fist example of rare-earth organometallic complex, the chemistry of rare-earth organometallic complexes has had a great advance during the past sixty years. A variety of Cp containing rare-earth metal complexes, including mono-Cp, bis-Cp, and tri-Cp complexes, have been synthesized. Variation of the size of substituent on Cp ring, introducing the nitrogen or oxygen containing pendant arm to Cp ring or using ansa bis-Cp ligands make the synthesis and stabilization of these three types of rare-earth metal Cp complexes available. The Cp related ligands, such as indenyl and fluorenyl, also have been applied for the rare-earth organometallic complexes. From 1990's, there was a tendency to explore the rare-earth organometallic complexes with ancillary ligands beyond Cp and its derivatives in order to search for more efficient rare-earth metal catalysts. Non-Cp ligands, such as biphenolates, β-diketiminates, amidinates, guanidinates, etc. have been introduced into the chemistry of rare-earth organometallic complexes, and a larger number of non-Cp rare-earth organometallic complexes have been synthesized and characterized. The application of non-cyclopentadienyl ligands not only resulted in the rare-earth organometallic complexes with new structural features, but also the catalysts with high activity and high selectivity for the polymer synthesis and organic synthesis. The rare-earth organometallic complexes catalyze homo-and co-polymerization of olefins as well as specific polymerization of dienes and polar monomers. The discovery of the catalytic system composed of the neutral rare-earth metal dialkyls/borate enables to synthesize some interesting polymers which are difficult to be prepared by using other catalytic system. The rare-earth organometallic complexes are also able to catalyze some important organic reactions, such as hydroamination, hydrophosphinylation, and hydroalkoxylation, etc. Different from the late-translation metal catalyzed organic reactions, most of the rare-earth metal catalyzed ones do not involve oxidative addition and reductive elimination steps. The review describes some important developments of the chemistry of rare-earth organometallic complexes in the past sixty years.

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Yttrium‐Amidopyridinate Complexes: Synthesis and Characterization of Yttrium‐Alkyl and Yttrium‐Hydrido Derivatives

Cited by 40 publications

References 89 publications

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

Molecular Rare‐Earth‐Metal Hydrides in Non‐Cyclopentadienyl Environments

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

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