Bis(<i>m</i>-terphenyl)silanes

Schröder, Artem; Lork, Enno; Beckmann, Jens

doi:10.1021/om5009082

Cited by 5 publications

(5 citation statements)

References 67 publications

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“…Instead, 3S and 3Se show a widening of the O(1)–Si(1)–C(10) angle to 120.6(2)° and 121.9(2)°, respectively. Such large deviations from the ideal tetrahedral angle while retaining the coordination number 4 are very rare and usually only observed when very bulky substituents are attached to the central atom . The silanol 5-Ph 2 P(O)-Ace-6-SiMe 2 OH ( 3O ) showing the large P/Si out-of-plane displacement lacks such a dramatic widening of the O(1)–Si(1)–C(10) angle (112.76(7)°).…”

Section: Resultsmentioning

confidence: 58%

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

et al. 2015

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The synthesis and characterization of the 5-diphenylphosphinoacenaphth-6-yl-silanes 5-Ph 2 P-Ace-6-SiMe 2 H (1), 5-Ph 2 P(S)-Ace-6-SiMe 2 H (1S), 5-Ph 2 P(Se)-Ace-6-SiMe 2 H (1Se), and 5-Ph 2 P-Ace-6-SiMe 2 Cl (2) as well as of the 5-diphenylphosphinoacenaphth-6-yl-silanols 5-Ph 2 P-Ace-6-SiMe 2 OH (3), 5-Ph 2 P(O)-Ace-6-SiMe 2 OH (3O), 5-Ph 2 P(S)-Ace-6-SiMe 2 OH (3S), and 5-Ph 2 P(Se)-Ace-6-SiMe 2 OH (3Se) are reported. Due to steric congestion in the bay area, the substituents in peri-positions are affected by repulsion, out-of-plane deflection, and distortion of the spatial arrangement to various extents. The peri-interaction energy associated with the steric congestion of these and a number of previously known reference compounds was computationally estimated with a set of isodesmic reactions. The organo-H-silanes 1, 1S, and 1Se possess very weak intramolecular hydrogen bridges of the types Si−H···P and Si−H···EP (E = S, Se), whereas the organosilanols 3O, 3S, and 3Se contain medium-strength hydrogen bonds of the type Si−OH···EP (E = O, S, Se). These hydrogen bonds and those of related model complexes H 3 SiOH···(E)PH 3 were analyzed applying real-space bonding indicators derived from the electron and pair densities using the atoms-in-molecules and electron localizability indicator space-partitioning schemes as well as natural population analysis and natural bond orbital analyses.

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Section: Resultsmentioning

confidence: 58%

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

et al. 2015

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“…These values are reproduced within 3° by DFT calculation . The fluorophosphonium ions 3 and 5 are isoelectronic with the neutral fluorosilanes R 2 Si(F)H and R 2 SiF 2 ( R =2,6‐Mes 2 C 6 H 3 ), which show somewhat smaller C−Si−C bond angles [129.4(2) and 129.7(1)°] . Despite considerable effort, no single crystals of 2 were obtained.…”

Section: Methodsmentioning

confidence: 99%

“…[16] The fluorophosphonium ions 3 and 5 are isoelectronic with the neutral fluorosilanes R 2 Si(F)H andR 2 SiF 2 (R = 2,6-Mes 2 C 6 H 3 ), whichs how somewhat smaller CÀSiÀC bond angles [129.4(2) and1 29.7(1)8]. [17] Despite considerable effort, no single crystalso f2 were obtained. The calculated gas phase structure of 2 gives rise to aC ÀPÀCa ngle (120.48)t hat lies in between 1 and 3 ( Figure 2).…”

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confidence: 99%

Functionalized Fluorophosphonium Ions

Olaru

Schröder

Albers

et al. 2019

Chemistry A European J

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Efforts to preparea ne lusive donor-free phosphenium ion, [R 2 P] + ,l ed us to synthesize functionalized fluorophosphonium cations of the type [R 2 P(F)X] + (X = SiEt 3 ,H ,F ), which were obtained from the relatedn eutral fluorophosphines R 2 PF and R 2 PF 3 upon protonation and reaction with solvated [Et 3 Si] + ions (R = 2,6-Mes 2 C 6 H 3 ). The hypothetical reductivee limination of [R 2 P(F)SiEt 3 ] + and [R 2 P(F)H] + affording [R 2 P] + ,E t 3 SiF and HF,r espectively, was calculated to be endothermic by 40.1 and 190.6 kJ mol À1

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“…Steric congestion of the aromatic rings is also the reason why the C–Si–C angle of 2c [113.8(4)°] is identical within the experimental error with that of Mes 2 SiH 2 [114.16(7)°] and slightly larger than those of 2a [110.2(3)°], 2b [110.62(8)°], and 5c [111.4(4)°]. It is to note that even larger C–Si–C angles were found recently in the bis( m ‐terphenyl)silane (2,6‐Mes 2 C 6 H 3 ) 2 SiH 2 [128.4(1)°] . The halogen atoms have again a significant influence of the 29 Si NMR chemical shifts, which follow a different trend that in the aryldimethylsilanes and diaryltetramethyldisilanes discussed above.…”

Section: Resultsmentioning

confidence: 57%

Reactivity of 2,6‐Dihalophenyl Lithium Reagents Towards Chlorosilanes. Synthesis and Structure of 2,3‐ and 2,6‐Dihalophenyl(di‐)silanes

Schröder

Denhof

Lork

et al. 2018

Zeitschrift anorg allge chemie

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The reaction of 2,6-dihalophenyllithium 2,6-X 2 C 6 H 3 Li (X = F, Cl, Br) with the chlorosilanes ClMe 2 SiSiCl 2 Me, SiCl 4 , and HSiCl 3 afforded the diaryldisilanes (2,6-X 2 C 6 H 3 SiMe 2 ) 2 [X = F (1a), Cl (1b), Br (1c)] and the diaryl-and triarylsilanes (2,6-X 2 C 6 H 3 ) 2 SiCl 2 [X = F (3a), Cl (3a)], (2,3-Br 2 C 6 H 3 ) 2 SiCl 2 (4c), (2,6-F 2 C 6 H 3 ) 3 SiH (6a), and (2,6-X 2 C 6 H 3 ) 2 Si(H)Cl [X = Cl (7b), Br (7c)], respectively. The formation of 4c was rationalized on the basis of an equilibrium that exists * Prof. Dr. J. Beckmann E-Mail: j.beckmann@uni-bremen.de [a] 1034 between the aryllithium isomers 2,6-Br 2 C 6 H 3 Li and 2,3-Br 2 C 6 H 3 Li . Reduction of 3a, 3b, 4c, 7b, and 7c using LiAlH 4 provided the diarylsilanes (2,6-X 2 C 6 H 3 ) 2 SiH 2 [X = F (2a), Cl (2b), Br (2c)] and (2,3-Br 2 C 6 H 3 ) 2 SiH 2 (5c), respectively. The products were characterized by multinuclear NMR spectroscopy ( 1 H, 13 C, 19 F, 29 Si) and in case of 1a, 1b, 2a, 2b, 2c, 5c, and 6a also by X-ray crystallography.

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Bis(m-terphenyl)silanes

Abstract: The synthesis and full characterization of the first bis(mterphenyl)silanes, namely, (2,6-Mes 2 C 6 H 3 ) 2 SiF 2 , (2,6-Mes 2 C 6 H 3 ) 2 SiHF, and (2,6-Mes 2 C 6 H 3 ) 2 SiH 2 , is reported.

Cited by 5 publications

References 67 publications

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

Functionalized Fluorophosphonium Ions

Reactivity of 2,6‐Dihalophenyl Lithium Reagents Towards Chlorosilanes. Synthesis and Structure of 2,3‐ and 2,6‐Dihalophenyl(di‐)silanes

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