An Acyclic Imino‐Substituted Silylene: Synthesis, Isolation, and its Facile Conversion into a Zwitterionic Silaimine

Inoue, Shigeyoshi; Leszczyńska, Kinga

doi:10.1002/anie.201203257

Cited by 102 publications

(78 citation statements)

References 97 publications

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“…The N‐heterocyclic imine‐substituted silylene XIV was reported by us in 2012 . The pronounced silylene character of XIV , which was supported by density functional theory (DFT) calculations showing a HOMO dominated by the lone pair of electrons on Si, was demonstrated experimentally by ready formation of a borane adduct.…”

Section: Introductionmentioning

confidence: 71%

NHC‐Stabilised Silyliumylidene Ions

Powley

Inoue

2019

The Chemical Record

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Donor‐stabilised silyliumylidene ions, from the parent [R−Si:]+, are a class of low‐valent silicon species which have received increasing research interest in the last several years. This interest began in the fundamental synthesis and characterisation of these compounds, but has since started to include more investigation into their further reactivity after several stable NHC‐stabilised silyliumylidene ions were reported. This personal account briefly discusses the history of the still‐young field of silyliumylidene ions followed by a more detailed discussion of published work from our group on the further development of silyliumylidene chemistry over the last four years.

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Section: Introductionmentioning

confidence: 71%

NHC‐Stabilised Silyliumylidene Ions

Powley

Inoue

2019

The Chemical Record

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“…S16 †). We conceived that this might hint towards a significant 1-germa-2-azaallene character of 3 resembling the 1-sila-2-azaallene nature reported for the tris( pentafluorophenyl)borane adduct of the iminosilylene V 16 (Fig. 1, adduct not shown).…”

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confidence: 71%

Isolation of a germanium(ii) cation and a germylene iron carbonyl complex utilizing an imidazolin-2-iminato ligand

Ochiai

Franz

et al. 2015

Dalton Trans.

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“…2). 31 Herein we report the synthesis and characterization of the hitherto unknown bis(2,6-diisopropylphenyl)imidazolin-2-imino aluminium dihydride {μ-LAlH 2 } 2 2 and its reactivity as a hydride transfer reagent.…”

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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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An Acyclic Imino‐Substituted Silylene: Synthesis, Isolation, and its Facile Conversion into a Zwitterionic Silaimine

Cited by 102 publications

References 97 publications

NHC‐Stabilised Silyliumylidene Ions

NHC‐Stabilised Silyliumylidene Ions

Isolation of a germanium(ii) cation and a germylene iron carbonyl complex utilizing an imidazolin-2-iminato ligand

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

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