Countercation Effect on Reactivity of<i>o</i>‐(Fluorodimethylsilyl)phenyl Anion

Kawachi, Atsushi; Teranishi, Takuya; Deguchi, Takuma; Yamamoto, Yohsuke

doi:10.1002/hc.21062

Cited by 4 publications

(6 citation statements)

References 19 publications

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“…12° from linearity, and there is a relatively close approach between the centroid of the flanking aryl ring nearest to zinc of 2.982 Å. The Zn–Me distance in 3 is 1.950(4) Å and is slightly longer than the Zn–Me distance in dimethylzinc, 1.927(6) Å, but well within the range of previously published dialkylzinc compounds (range 1.930–1.982 Å). − …”

Section: Resultssupporting

confidence: 80%

“…The reaction of Pb(Ar Me 6 ) 2 with ZnMe 2 produced 4 (Figure ) via ligand exchange. The zinc atom is linearly coordinated with an angle of 180.0°, and the Zn–C bond lengths are 1.941(8) and 1.925(7) Å for the methyl and aryl groups, respectively, and fall within the range of previously published dialkylzinc molecules (range 1.930–1.982 Å). − …”

Section: Resultssupporting

confidence: 65%

“…The terphenyl ligands provide steric bulk, which shields the compound against association. The Zn–C distances to the disordered ethyl carbons C3 and C3B are essentially identical at 1.998(9) and 1.998(11) Å, which is slightly longer than the range of published two-coordinate dialkylzinc compounds (range 1.930–1.982). − The Ge–Zn bond length of 2.3839(11) Å is similar to the sum of the single-bond covalent radii of germanium (1.22 Å) and zinc (1.18 Å) and is close to that in the homoleptic bis-germyl species Zn{Ge(SiMe 3 ) 3 } 2 (2.382 Å), , which is the only previously structurally characterized compound with a Ge–Zn bond in which the zinc atom is two-coordinate.…”

Section: Resultsmentioning

confidence: 73%

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Molecular Zinc Species with Ge–Zn and Sn–Zn Bonds: A Reversible Insertion of a Stannylene into a Zinc–Carbon Bond

et al. 2016

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The tetrylenes Ge(Ar Me 6 ) 2 and Sn(Ar Me 6 ) 2 (Ar Me 6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6-(CH 3 ) 3 ) 2 ) reacted with dimethylzinc to afford the insertion products (Ar Me 6 ) 2 Ge-(Me)ZnMe ( 1) and (Ar Me 6 ) 2 Sn(Me)ZnMe (3), which feature Ge−Zn and Sn−Zn bonds as well as two-coordinate zinc atoms. Crystals of 1 were found to be unsuitable for X-ray crystallography, so the ethyl-substituted (Ar Me 6 ) 2 Ge(Et)ZnEt (2) was synthesized in a parallel way to provide crystals suitable for X-ray studies. These showed the structure to be similar to that of 3. The reaction of Pb(Ar Me 6 ) 2 with dimethylzinc yielded Ar Me 6 ZnMe with a linearly coordinated zinc atom via ligand exchange but no characterizable, new lead product was obtained. The reaction of Sn(Ar Me 6 ) 2 with dimethylzinc is reversible in hydrocarbon solution at room temperature and displayed a dissociation constant K diss and a ΔG diss of 0.0028(5) and 14(4) kJ mol −1 at 298 K, respectively. Compounds 1−4 were characterized by NMR and IR spectroscopy as well as by X-ray crystallography for 1, 3, and 4.

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Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 65%

Section: Resultsmentioning

confidence: 73%

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Molecular Zinc Species with Ge–Zn and Sn–Zn Bonds: A Reversible Insertion of a Stannylene into a Zinc–Carbon Bond

et al. 2016

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“…Li–Br exchange of o -(fluorosilyl)bromobenzenes 5 and 6 using tert -BuLi in Et 2 O at −78 °C affords aryllithium 7 and 8 , which were subsequently reacted with Mes 2 BF to yield 1 and 2 , respectively (Scheme ). , 1 and 2 were obtained as colorless crystals via recrystallization from hexane.…”

Section: Resultsmentioning

confidence: 99%

“…In our previous work, we constructed two B/Si bidentate Lewis acids, o -(fluorosilyl)(dimesitylboryl)benzenes 1 and 2 , using a o -phenylene skeleton (Chart ). , In this context, we have extended this chemistry to the difluorosilyl system, o -(difluorosilyl)(dimesitylboryl)benzenes 3 and 4 . Herein, we report the preparation, structure, Lewis acidity, and dynamic behavior of monofluorosilyl and difluorosilyl systems 1–4 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of B/Si Bidentate Lewis Acids, o-(Fluorosilyl)borylbenzenes and o-(Difluorosilyl)borylbenzenes, and Their Fluoride Ion Affinities

et al. 2022

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Herein, we report detailed studies on a series of o -(silyl)(boryl)benzenes ( 1–4 ), in which the two Lewis acid centers consisting of silicon and boron atoms are linked via an o -phenylene skeleton. o -(Fluorosilyl)(dimesitylboryl)benzenes 1 and 2 were prepared by the reaction of fluorodimesitylborane with [ o -(fluorodimethylsilyl)phenyl]lithium ( 7 ) and [ o -(fluorodiphenylsilyl)phenyl]lithium ( 8 ), respectively. o -(Difluorosilyl)(dimesitylboryl)benzenes 3 and 4 were also prepared by the reaction of fluorodimesitylborane with o -{[di(methoxy)methylsilyl]phenyl}lithium ( 11 ) and o -{[di(methoxy)phenylsilyl]phenyl}lithium ( 12 ), respectively, and their subsequent treatment with HF·pyridine. Compounds 1–4 readily capture a fluoride ion in the presence of 18-crown-6 or [2.2.2]cryptand to afford their corresponding μ-fluoro-bridged ate complexes ( 15–18 ). The structures of 15–18 were revealed by NMR spectroscopy and X-ray crystallography. DFT studies and natural bond orbital analysis of 15–18 were conducted to elucidate the nature of the Si–F and B–F bonding interactions in the μ-fluoro-bridges. The fluoride ion affinities of 1–4 were investigated by 1 H NMR spectroscopy to monitor their competitive reactions. The dynamic behaviors of 15–18 at variable temperatures were monitored using 19 F NMR spectroscopy.

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Fluorescence and phosphorescence of a series of silicon-containing six-membered-ring molecules

Nakashima

Shimada

Kurihara

et al. 2016

Journal of Organometallic Chemistry

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Various silicon-containing six-membered-ring molecules were synthesized by Pd-catalyzed coupling reaction of 1,2-bis(dimethylsilyl)arenes with 1,2-diiodoarenes in moderate yields. Their optical properties were investigated via UV-vis absorption, fluorescence and phosphorescence spectroscopies, which indicated that the σ*-π* conjugated system expanded owing to the silicon © 2015. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/ atoms. Some of the compounds exhibited enhanced luminescence, larger Stokes shift, and phosphorescence in comparison with 9,9,10,10-tetramethyl-9,10-dihydroanthracene. Density functional theory (DFT) studies were also performed to investigate the photophysical properties of the compounds.

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Countercation Effect on Reactivity ofo‐(Fluorodimethylsilyl)phenyl Anion

Cited by 4 publications

References 19 publications

Molecular Zinc Species with Ge–Zn and Sn–Zn Bonds: A Reversible Insertion of a Stannylene into a Zinc–Carbon Bond

Molecular Zinc Species with Ge–Zn and Sn–Zn Bonds: A Reversible Insertion of a Stannylene into a Zinc–Carbon Bond

Synthesis of B/Si Bidentate Lewis Acids, o-(Fluorosilyl)borylbenzenes and o-(Difluorosilyl)borylbenzenes, and Their Fluoride Ion Affinities

Fluorescence and phosphorescence of a series of silicon-containing six-membered-ring molecules

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