Recent progress in transition metal complexes supported by multidentate ligands featuring group 13 and 14 elements as coordinating atoms

Komuro, Takashi; Nakajima, Yumiko; Takaya, Jun; Hashimoto, Hisako

doi:10.1016/j.ccr.2022.214837

Cited by 34 publications

(19 citation statements)

References 219 publications

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“…Organosilicon compounds are stable, nontoxic, and easy-handling, enabling them to be commonly employed in materials science, medicinal synthesis, and chemical transformation. , Unlike carbon, silicon has a large atomic radius and a low electronegativity, which usually acts as an electrophilic site or a protecting group (Scheme a). , The unique α/β silicon effect of organosilicon compounds makes them valuable reactants in hydrosilylation, cross-coupling, and other reactions. – Moreover, silicon plays a crucial role in forming Si–M bonds with metal centers and serving as a catalyst in various reactions. – …”

Section: Introductionmentioning

confidence: 99%

Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

Li,

Liang,

Liu

et al. 2023

ACS Catal.

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Transition-metal complexes with Si−M bonds are important catalysts for hydrosilylation and hydrogenation reactions. However, the function of the ligated silicon atom in the organosilicon metal catalysts remains unknown. Herein, we unravel the intriguing role of silyl and silane types of active modes in the Si−Ni complexcatalyzed selective hydrogenation of alkyne. Comprehensive density functional theory calculations were performed to investigate the nickel hydride insertion, silicon hydride migration, H 2 metathesis, and H 2 oxidative addition mechanisms. The results suggest that the silyl and silane types of active species display distinct catalytic properties in the hydrogenation reaction. During the hydrogenation of alkyne, Ni−H insertion heavily relies on the highly active nickel hydride in the silyl−nickel intermediate. Conversely, in the hydrogenation of stilbene, the driving force is the oxidation of the Ni(0) center in the silane−nickel intermediate. The revealed roles of silicon as silyl and silane during the catalysis well explained the E/Z stereoselectivity and chemoselectivity between the olefin product and the alkane product for the Si−Ni-catalyzed hydrogenation of alkyne. Furthermore, we explored the structure− activity relationship of bifunctional sites that incorporate group IVA elements (C, Si, Ge, and Sn). Hydrogenation of both alkynes and olefins can be accomplished via analogous silyl− and silane−metal transformations. Our theoretical study provides valuable insights into the mechanism and role of silicon in Si−Ni-catalyzed hydrogenation and would be helpful for future catalyst design with ligands containing group IVA elements.

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Section: Introductionmentioning

confidence: 99%

Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

Li,

Liang,

Liu

et al. 2023

ACS Catal.

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“…The organolanthanide complexes have been attracting increasing attention in recent years due to their novel structural features and potential applications in small-molecule activation and catalysis. − Although this area is under vigorous research, the chemistry of organolanthanide is dominated by compounds containing essentially electrostatic coordination bonds between the cationic lanthanide (Ln) centers and anionic electronegative p -block elements, such as halides, O, N, and S . In particular, the investigation of organolanthanide complexes with heavier tetrel element ligands is still in scarce conditions and much of it lags behind the developments of the chemistry of heavier tetrel compounds themselves and their transition-metal complexes; − for them the structural features, , spectroscopic properties, , and reactivities , through the whole column of tetrel elements have been systematically documented.…”

Section: Introductionmentioning

confidence: 99%

Structural, Spectroscopic, and Bonding Analyses of La(III)/Ce(III)-Tetrel Ate-Complexes

Pan

Fang

et al. 2023

Inorg. Chem.

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In comparison with the research of transition-metal-tetrel complexes, the chemistry of lanthanide tetrel complexes, especially for these bearing heavier tetrel element ligands, is still relatively underexplored. In this research, K[Cp 3 Ln(III)CH 2 Ph], [(DME) 3 Li][Cp 3 Ln(III)GePh 3 ], and [(DME) 3 Li][Cp 3 Ln(III)SnPh 3 ] [Ln(III) = La(III), Ce(III)] have been synthesized by reacting [(DME) 3 Na][Cp 3 La(μ-Cl)LaCp 3 ] or Cp 3 Ce(THF) with alkali metal alkyl, germyl, and stannyl reagents. Additionally, [(DME) 3 Li][Cp 3 Ce(III)SnPh 3 ] is the first example of Ce(III)−Sn bond containing complex. All the obtained early Ln(III) tetrel ate-complexes were structurally analyzed by single-crystal X-ray diffraction. The formal shortness ratios of the Ln(III)−C, Ln(III)−Ge, and Ln(III)−Sn bonds are in the range of 1.03−1.11. Together with the previously reported [(DME) 3 Li][Cp 3 Ln-(III)SiPh 3 ], a group of tetrel (up to Sn) lanthanocene ate-complexes with an analogous coordination pattern are presented. Computational studies suggest the strongly polarized nature of the Ln(III)−E (E = C, Si, Ge, Sn) bonds in these complexes, with 77−85% atomic orbital contribution from tetrel elements and 15−23% atomic orbital contribution from Ln(III). The UV−vis measurements of this series of complexes show that the characteristic absorptions are hypsochromically shifted for Ln(III) heavier tetrel complexes in comparison to their lighter congeners. Moreover, the HOMOs, in which the Ln(III)−E σ-bonding orbitals are the dominant components, of these series complexes act as donor orbitals of the major electron transitions, as being disclosed by the time-dependent density functional theory analysis.

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“…Sigma-accepting (or Z -type) ligands incorporating Lewis acidic E( X ) n functionalities have become prominent in the past few years because of their ability to interact with transition metal (TM) centers to afford complexes with unusual coordination geometries and high reactivity. , One commonly used approach to stabilize TM → E( X ) n interactions involves the use of peripheral P donors to form pincer phosphine ligands P–E( X ) n –P. − As the archetypal Lewis acids, group 13 elements, and in particular B, have been the focus of considerable attention and a rich chemistry has developed for B(alkyl/aryl)-derived pincers. − In contrast, far fewer examples of P–Al(X)–P ligands are known, and these are largely restricted to X = halide derivatives. − In one early example, Bourissou and co-workers showed that attempts to generate Cu→(P–Al(Cl)–P) and Au→(P–Al(Cl)–P) complexes through coordination of ( o - i Pr 2 PC 6 H 4 ) 2 AlCl to Cu(I) and Au(I) halide precursors instead resulted in halide migration from the coinage metal to Al to afford zwitterionic products as a result of the high Lewis acidity of the AlCl moiety. , …”

Section: Introductionmentioning

confidence: 99%

“… 1 , 2 One commonly used approach to stabilize TM → E( X ) n interactions involves the use of peripheral P donors to form pincer phosphine ligands P–E( X ) n –P. 3 − 6 As the archetypal Lewis acids, group 13 elements, and in particular B, have been the focus of considerable attention and a rich chemistry has developed for B(alkyl/aryl)-derived pincers. 7 − 9 In contrast, far fewer examples of P–Al(X)–P ligands are known, and these are largely restricted to X = halide derivatives.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands

et al. 2022

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Reaction of [Ru(C6H4PPh2)2(Ph2PC6H4AlMe(THF))H] with CO results in clean conversion to the Ru−Al heterobimetallic complex [Ru(AlMePhos)(CO)3] (1), where AlMePhos is the novel P–Al(Me)–P pincer ligand (o-Ph2PC6H4)2AlMe. Under photolytic conditions, 1 reacts with H2 to give [Ru(AlMePhos)(CO)2(μ-H)H] (2) that is characterized by multinuclear NMR and IR spectroscopies. DFT calculations indicate that 2 features one terminal and one bridging hydride that are respectively anti and syn to the AlMe group. Calculations also define a mechanism for H2 addition to 1 and predict facile hydride exchange in 2 that is also observed experimentally. Reaction of 1 with B(C6F5)3 results in Me abstraction to form the ion pair [Ru(AlPhos)(CO)3][MeB(C6F5)3] (4) featuring a cationic [(o-Ph2PC6H4)2Al]+ ligand, [AlPhos]+. The Ru–Al distance in 4 (2.5334(16) Å) is significantly shorter than that in 1 (2.6578(6) Å), consistent with an enhanced Lewis acidity of the [AlPhos]+ ligand. This is corroborated by a blue shift in both the observed and computed νCO stretching frequencies upon Me abstraction. Electronic structure analyses (QTAIM and EDA-ETS) comparing 1, 4, and the previously reported [Ru(ZnPhos)(CO)3] analogue (ZnPhos = (o-Ph2PC6H4)2Zn) indicate that the Lewis acidity of these pincer ligands increases along the series ZnPhos < AlMePhos < [AlPhos]+.

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Recent progress in transition metal complexes supported by multidentate ligands featuring group 13 and 14 elements as coordinating atoms

Cited by 34 publications

References 219 publications

Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

Structural, Spectroscopic, and Bonding Analyses of La(III)/Ce(III)-Tetrel Ate-Complexes

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands

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