A Tin Analogue of Carbenoid: Isolation and Reactivity of a Lithium Bis(imidazolin‐2‐imino)stannylenoid

Ochiai, Tetsuyuki; Franz, Daniel; Wu, Xiao‐Nan; Irran, Elisabeth; Inoue, Shigeyoshi

doi:10.1002/anie.201602178

Cited by 39 publications

(26 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Very recently, our group described the bisiminochlorostannate 58 which forms by the reaction of L Dip NLi with half an equivalent of SnCl 2 Á1,4-dioxane (Scheme 14). 27 The 119 Sn NMR spectrum of 58 (thf-d 8 ) shows a resonance at À18 ppm that is shifted to a lower field in comparison to common monomeric trigonal pyramidal-coordinate 1,3-diketiminato tin(II) chlorides (À118 ppm to À337 ppm). 28 The XRD analysis of 58 reveals a butterfly-shaped four-membered SnN 2 Li stannacycle with no bonding interaction between the Sn atom and the Li atom (Fig.…”

Section: Tin Complexesmentioning

confidence: 99%

Applications of N-heterocyclic imines in main group chemistry

2016

Self Cite

View full text Add to dashboard Cite

The imidazolin-2-imino group is an N-heterocyclic imino functionality that derives from the class of compounds known as guanidines. The exocyclic nitrogen atom preferably bonds to electrophiles and its electron-donating character is markedly enhanced by efficient delocalization of cationic charge density into the five-membered imidazoline ring. Thus, this imino group is an excellent choice for thermodynamic stabilization of electron-deficient species. Due to the variety of available imidazoline-based precursors to this ligand, its steric demand can be tailored to meet the requirements for kinetic stabilization of otherwise highly reactive species. Consequently, it does not come as a surprise that the imidazolin-2-iminato ligand has found widespread applications in transition-metal chemistry to furnish pincer complexes or "pogo stick" type compounds. In comparison, the field of main-group metal compounds of this ligand is still in its infancy; however, it has received growing attention in recent years. A considerable number of electron-poor main-group element species have been described today which are stabilized by N-heterocyclic iminato ligands. These include low-valent metal cations and species that are marked by formerly unknown bonding modes. In this article we provide an overview on the present chemistry of main-group element compounds of the imidazolin-2-iminato ligand, as well as selected examples for the related imidazolidin- and benzimidazolin-2-imino system.

show abstract

Section: Tin Complexesmentioning

confidence: 99%

Applications of N-heterocyclic imines in main group chemistry

2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…Molecular structures have been determined for amino‐ ( 1 ), alkoxy‐ ( 2 ), and fluorine‐substituted ( 3 ) silylenoids as shown in Scheme . Less attention has been focused on germylenoids and stannylenoids, while molecular structures of tetrylenoids 4 , 5 , 6 , and 7 have been studied by X‐ray crystallography (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

“…Heavy tetrylenoids R 2 EXM (E=Si, Ge, and Sn) have been prepared by various methods, including reduction of R 2 EXX′ using alkali metals, or lithium naphthalenide, the desilylation of R 2 E(X)SiMe 3 with t ‐BuOK, tin–lithium exchange reaction of R 2 E(X)SnMe 3 using an alkyllithium, and reactions of inorganic divalent tetrylenes EX 2 with RLi ,. No formation of tetrylenoids through the direct reaction between the corresponding tetrylene and a metal halide has been reported to date, while the reversibility between R 2 EXM and R 2 E: + MX has been assumed, sometimes without any evidence.…”

Section: Methodsmentioning

confidence: 99%

Reversible Stannylenoid Formation from the Corresponding Stannylene and Cesium Fluoride

Yan

Xiao

et al. 2016

Angewandte Chemie

View full text Add to dashboard Cite

A fluorostannylenoid (Cs+[R2SnF]− (9), R2=(TMS)2CCH2CH2C(TMS)2) was prepared by reacting a stable dialkylstannylene (R2Sn (8), R2=(TMS)2CCH2CH2C(TMS)2) with cesium fluoride at room temperature in THF. While 9 is stable in THF and DME, removal of the solvent leads to the regeneration of stannylene 8. No reaction occurred when 8 was treated with CsF in a hydrocarbon solvent. Addition of dibenzo‐21‐crown‐7 ether to the THF solution of stannylenoid 9 followed by usual workup affords the corresponding crystalline stannylenoid crown ether complex, the X‐ray structural analysis of which revealed a fluorine‐bridged contact ion‐pair structure. The reaction of 9 with excess phenylacetylene gives the corresponding di(phenylethynyl)stannane.

show abstract

“…Their formation is promoted by the delocalization of positive charge density into the imidazoline ring . Notably, this imino system was also implemented in the bis(imino)germylene F and the bis(imino)stannylenoid G and the strongly related imidazolidine‐2‐iminato ligand (saturated in the ligand backbone) has been successfully used for the synthesis of a phosphorus mononitride radical cation . These studies reveal that the imidazolin‐2‐imino group is particularly efficient in the stabilization of electron‐deficient species.…”

Section: Figurementioning

confidence: 99%

Isolation and Structure of Germylene‐Germyliumylidenes Stabilized by N‐Heterocyclic Imines

et al. 2016

Self Cite

View full text Add to dashboard Cite

The ditopic germanium complex FGe(NIPr)2 Ge[BF4 ] (3[BF4 ]; IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is prepared by the reaction of the amino(imino)germylene (Me3 Si)2 NGeNIPr (1) with BF3 ⋅OEt2 . This monocation is converted into the germylene-germyliumylidene 3[BAr(F) 4 ] [Ar(F) =3,5-(CF3 )2 -C6 H3 ] by treatment with Na[BAr(F) 4 ]. The tetrafluoroborate salt 3[BF4 ] reacts with 2 equivalents of Me3 SiOTf to give the novel complex (OTf)(GeNIPr)2 [OTf] (4[OTf]), which affords 4[BAr(F) 4 ] and 4[Al(OR(F) )4 ] [R(F) =C(CF3 )3 ] after anion exchange with Na[BAr(F) 4 ] or Ag[Al(OR(F) )4 ], respectively. The computational, as well as crystallographic study, reveals that 4(+) has significant bis(germyliumylidene) dication character.

show abstract

A Tin Analogue of Carbenoid: Isolation and Reactivity of a Lithium Bis(imidazolin‐2‐imino)stannylenoid

Cited by 39 publications

References 75 publications

Applications of N-heterocyclic imines in main group chemistry

Applications of N-heterocyclic imines in main group chemistry

Reversible Stannylenoid Formation from the Corresponding Stannylene and Cesium Fluoride

Isolation and Structure of Germylene‐Germyliumylidenes Stabilized by N‐Heterocyclic Imines

Contact Info

Product

Resources

About