Fluorine functionalized compounds of group 13 elements

Singh, Sanjay; Roesky, Herbert W.

doi:10.1016/j.jfluchem.2006.07.018

Cited by 10 publications

(6 citation statements)

References 54 publications

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“…Since the report of LAl 5 in 2000, we have developed its amazing chemistry. We reviewed these results in 2004; therefore, the progress made by us since then will be described in more detail here after giving a summary of our earlier work.…”

Section: Aluminum(i) Chemistrymentioning

confidence: 99%

The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)

2008

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Although tetrameric Al(I) compounds have been known for a long time, the monomeric Al(I) compounds that are analogous to carbenes are very recent entrants in Al(I) chemistry. They possess novel structural features and exhibit distinct reactivity. This has resulted in the isolation and characterization of various unusual aluminum(III) compounds such as the aluminatetrazoles and aluminacyclopropenes. In comparison to the recent emergence of monomeric aluminum(I) compounds, stable silylenes and germylenes (carbene analogues of silicon and germanium) were recognized much earlier. This led to the evolution of the Si(II) and Ge(II) chemistry that at times surpasses the sophistication achieved in divalent carbon chemistry. Thus, while carbon lacks an example of a stable chlorocarbene (LCCl), for silicon there is one example of LSiCl, and for germanium there are a fair number of LGeCl compounds. While reactivity studies on LSiCl are anticipated, the utility of RGeCl as a synthon is well documented. Exotic compounds such as a germanethioacid chloride, a germanium(II) hydride, and a germanium(II) hydroxide are some of the examples that were derived from LGeCl. Recent results from our laboratory at Göttingen have helped in the development of these interesting areas of research, and the present account summarizes our contributions to the chemistry of Al(I), Si(II), and Ge(II).

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Section: Aluminum(i) Chemistrymentioning

confidence: 99%

The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)

2008

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“…9,10 In a different field of applied science one finds chemical vapour deposition technology exploiting the thermodynamic properties of molecular aluminium hydrides for the purpose of creating composite materials. 1,[13][14][15] Aluminium hydrides are considered as fuel storagematerials with reasonable prospects in a hydrogen-based alternate energy-supply concept. 16,17 Moreover, the application of aluminium hydrides in the synthesis of low-valent aluminium compounds has been reported and III 18 ( Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

2014

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The reaction of bis(2,6-diisopropylphenyl)imidazolin-2-imine (LH, 1) with Me 3 N·AlH 3 furnishes {μ-LAlH 2 } 2 (2). The marked tendency of 2 to release its hydride substituents is ascribed to the strong electron-donor character of the imidazolin-2-iminato ligand. This is supported by its reactivity study and DFT calculations.In fact, compound 2 was further converted with Me 3 SiOTf, Me 2 S·BH 3 , Me 2 S·BBr 3 , and BX 3 (with X = Cl, Br, and I) into {μ-LAl(H)OTf} 2 (3), {μ-LAl(BH 4 ) 2 } 2 (4), and {μ-LAlX 2 } 2 (5, X = Br; 6, X = Cl; 7, X = I), respectively.For all new aluminium complexes the formulation as dimers was evidenced by high resolution mass spectrometry, as well as single-crystal X-ray diffraction analysis. A prominent structural motif of these compounds is the square-planar four-membered Al 2 N 2 ring with two bridging bulky imidazolin-2-imino moieties. IntroductionAluminium hydrides -versatile reagents with rich chemistry For many years, chemical synthesis has been gaining immense benefit from the distinct reactivity of the aluminium-hydrogen bond. The strong need for highly selective transformations, increased focus on safety considerations, and efficiency in handling and storage are only some reasons why we find the chemically rogue parent aluminium hydride tamed into more suitable forms today. A variety of hydridoalanes has been tailored and very often reactivity adjustment is realized by steric congestion at the aluminium centre and by attaching strongly electron-donating substituents to the aluminium atom. Furthermore, hydridoalanes are used in a diverse range of applications. For instance, the hydroalumination of carbonyl 1,2 and alkyne 3-7 functionalities is a common application for this class of compounds in organic synthesis. Though the intermediate aluminium species in these reactions are often elusive, the use of aluminium hydrides such as I 8 ( Fig. 1) that bear highly sophisticated ligands grants access to all types of isolatable and well-defined model complexes. Compound I can be categorized as an aluminium dihydride and is related to the parent aluminium trihydride by replacement of one hydride for an anionic ligand. Thus, an ancillary ligand may be introduced, and yet, two reactive functional groups at the metal centre are preserved for the purpose of follow-up chemistry. The β-diketimino group, in particular, has been a key ligand to a rich chemistry of respective aluminium dihydrides. 9-12 A prominent example is II (Fig. 1), which can View Article OnlineView Journal | View Issue be used for the activation of non-polar element-element bonds as demonstrated by its conversion with elemental sulphur or selenium. 9,10 In a different field of applied science one finds chemical vapour deposition technology exploiting the thermodynamic properties of molecular aluminium hydrides for the purpose of creating composite materials. 1,13-15Aluminium hydrides are considered as fuel storagematerials with reasonable prospects in a hydrogen-based alternate energy-supply concept. 16,17 Moreover, the...

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“…Recently, many research groups have made contributions to the development of air-stable Lewis acid metal complexes. [22][23][24][25] Kobayashi and coworkers developed a series of zirconium Lewis acid complexes with an air-stable Zr-O bond. The storable chiral zirconium catalysts are highly efficient for enantioselective Mannich-type, aza-Diels-Alder, aldol, and hetero Diels-Alder reactions.…”

Section: Development Of Air-stable Lewis Acid Metal Complexesmentioning

confidence: 99%

A mini-review on air-stable organometallic Lewis acids: synthesis, characterization, and catalytic application in organic synthesis

et al. 2012

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Organometallic Lewis acids play an important role in modern organic synthesis. How to design and synthesize highly efficient and recyclable organometallic Lewis acid catalysts that can be conveniently applied in chemical reactions are key issues for sustainable synthetic processes. In general, stronger acidity means higher catalytic activity for organometallic Lewis acids. However, with the rise in acidity, the compound becomes more susceptible to hydrolysis and cannot be recycled. Simultaneous improvement of the hygroscopic character and Lewis acidity/catalytic activity of organometallic Lewis acids is highly desirable from the standpoint of practical applications. In this mini-review, the history of air-stable organometallic Lewis acids is introduced, with emphasis on our research works on metallocene, organobismuth, and organoantimony Lewis acids to the aspects of synthesis, characterization and catalytic application in carbon-carbon bond (Friedel-Crafts acylation, Mukaiyama aldol reactions; allylation, cyclotrimerization, Mannich reactions, cross-condensation reactions) and carbon-heteroatom bond (acylation, S-S bond cleavage, glycosylation) formation reactions. In terms of stability, storage, versatile ability, high catalytic activity and chemo-/stereoselectivity, the complexes will find broad applications in organic synthesis.

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Fluorine functionalized compounds of group 13 elements

Cited by 10 publications

References 54 publications

The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)

The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

A mini-review on air-stable organometallic Lewis acids: synthesis, characterization, and catalytic application in organic synthesis

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