2,3,4-Tricarba-nido-hexaboranes(7) with a Bridging B−Ethyl−B Moiety

Wrackmeyer, Bernd; Schanz, Hans‐Jörg; Hofmann, Matthias; Schleyer, Paul von Ragué

doi:10.1002/(sici)1099-0682(199805)1998:5<633::aid-ejic633>3.3.co;2-4

Cited by 9 publications

(45 citation statements)

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“…The values of 1 J [ 117/119 Sn− 13 C] ( Table 5) and bond angles (C Sn C) 111.7 • and 110.9 • , enumerated from 1 J values [20,21] for trimethyltin and tri-n-butyltin derivatives, respectively, also confirm the proposed tetrahedral structure in noncoordinating solvent. Similarly, the values of δ 119 Sn (Table 7) are also consistent with earlier reports, describing tetrahedral geometry [22,23]. [24] as proposed in Fig.…”

Section: Multinuclear Nmrsupporting

confidence: 91%

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Sadiq‐ur‐Rehman

Shahid

Ali

et al. 2005

Heteroatom Chemistry

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Organotin(IV) complexes with general formula R4 − nSnLn have been synthesized by the reaction of tri‐ and diorganotin chlorides with sodium salt of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid in dry toluene, where RCH3, C2H5, n‐C4H9, C6H5, n = 1 or 2, and L = [ŌOCC(C6H5) CH(C6H4OCH3)]. Dimeric distannoxanes, [(R2SnOOCC(C6H5)CH‐(C6H4OCH3)2O]2, were synthesized by the reaction of acid with diorganotin oxides in 1:1 molar ratio. Multinuclear NMR (1H, 13C, 119Sn), infrared, mass, and Mössbauer spectral techniques have been used to ascertain their structures in solution and as solid. The spectroscopic results showed that triorganotin(IV) derivatives are 4‐coordinated monomers in noncoordinating solvents and 5‐coordinated polymers with bridging carboxylate groups in the solid state. However, diorganotin and dimeric compounds are 5‐coordinated in noncoordinating solvents while in the solid phase may have higher coordination. Biological screening tests showed that most of the compounds have significant activity against different bacteria and fungi. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:175–222, 2005; Published online in Wiley InterScience (http://www.interscience.wiley.com). DOI 10.1002/hc.20089

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Section: Multinuclear Nmrsupporting

confidence: 91%

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Sadiq‐ur‐Rehman

Shahid

Ali

et al. 2005

Heteroatom Chemistry

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“…Numerous studies have demonstrated that the intramolecular Si-H···B bridge can maintain the conformation of compounds simultaneously containing silicon and boron atoms. [37][38][39][40][41][42] In the present paper, we study the triel bond between ZX 3 (Z = B and Al; X = H and Me) and THMe 3 (T = Si, Ge and Sn). The T-H bond in THMe 3 acts as the Lewis base in the triel bond; thus this interaction is named triel-hydride triel bond, coining the name of halogenhydride halogen bond, [43] chalcogen-hydride chalcogen bond, [44] pnicogen-hydride pnicogen bond, [45] tetrelhydride tetrel bond [46] and lithium-hydride lithium bond.…”

Section: Introductionmentioning

confidence: 99%

Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)

Zhang

Wei

et al. 2018

Applied Organom Chemis

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Complexes between THMe3 (T = Si, Ge and Sn) and ZX3 (Z = B and Al; X = H and Me) have been characterized using MP2/aug‐cc‐pVTZ calculations. These complexes are chiefly stabilized by a triel–hydride triel bond with the T–H bond pointing to the π‐hole on the triel atom. The triel–hydride interaction is mainly attributed to the charge transfer from the T–H bond orbital to the empty p orbital of the triel atom. These complexes are very stable with a large interaction energy (>10 kcal mol−1) excluding THMe3···BMe3 (T = Si and Ge), indicating that the sp2‐hydridized triel atom has a strong affinity for the T–H bond. The formation of THMe3···BH3 results in proton transfer, characterized by conversion of orbital interaction and large charge transfer (ca 0.5e). The large deformation is primarily responsible for the abnormally greater interaction energy in THMe3···BH3 (>30 kcal mol−1) than in the AlH3 analogue. Methyl substitution on the triel atom weakens the triel–hydride interaction and causes a larger interaction energy in THMe3···AlMe3 with respect to its BMe3 counterpart. Most of these interactions possess characteristics of covalent bonds. Polarization makes a contribution to the stability of most complexes nearly equivalent to the electrostatic term.

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“…5 [8] and 6a [8] ), and a fairly complete set of important solution-state NMR spectroscopic data is not available at all. For instance, the magnitude of spin-spin coupling constants 1 J( 29 Si,13 C) for some diphenylsilyl-substituted carboranes [9] is smaller than expected at a first glance, considering the large magnitude of 1 J( 13 C, 1 H) in 1 [ 1 J( 13 C, 1 H) = 193 Hz] [10] or in mono-substituted ortho-carboranes. [10] This was attributed to high s electron density in the C-H hybrid orbital.…”

Section: Introductionmentioning

confidence: 99%

“…additional conclusive structural information, both by determination of chemical shifts and various spin-spin coupling constants. In all cases 3-6, the spin-spin coupling constants 1 J( 29 Si, 13 C) were measured, in most cases from 13 C satellites in the 29 Si NMR spectra. The 13 C(carborane) NMR signals are only slightly broadened owing to unresolved scalar 13 C- 11 B coupling ( 11 B: I = 3/2; 10 B: I = 3).…”

Section: Introductionmentioning

confidence: 99%

Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

Wrackmeyer

Klimkina

Milius

2012

Zeitschrift anorg allge chemie

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Non-cyclic and cyclic silyl-substituted 1,2-dicarba-closo-dodecaborane(12) derivatives were prepared mainly by salt elimination methods. Several known and new compounds were structurally characterized by X-ray analysis in the solid state and by mulinuclear magnetic resonance ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR) in solution. This includes the 1,2-bis(trimethylsilyl) and 1,2-bis(chlorodimethylsilyl) derivatives as examples for non-cyclic compounds and a series of 1,1,3,3-tetramethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-1080 disila-2-element-cyclopentanes (element = S, Se, Te). Numerous spinspin coupling constants were determined together with their signs. Molecular gas phase geometries for most compounds studied were optimized by calculations [B3Lyp/6-311+G(d,p)], and NMR parameters were calculated at the same level of theory. The conversion of silylsubstituted ortho-carboranes into their respective 7,8-dicarba-nido-undecaborate(1-) derivatives was explored successfully for several examples.In the presented work, we have set out to prepare the missing heavy homologues of 6a with sulfur (6b), selenium (6c) and tellurium (6d), starting from 4 or 5. Some aspects of the reactivity of 5 was addressed, and first attempts were made to convert some of the silyl-substituted carboranes into the respective 7,8-dicarba-nido-undecaborates(1-). The NMR spectra of 3-6 were measured ( 1 H, 11 B, 13 C, 29 Si, 77 Se, and 125 Te NMR), including the determination of absolute signs of spinspin coupling constants, if possible. The molecular structures of 3, 4, 6c, and 6d were determined by X-ray structural analysis, and the gas phase geometries of 3-6 were optimized [B3LYP/6-311+G(d,p)] followed by calculation of NMR parameters at the same level of theory (except of 6d). Results and Discussion Syntheses and NMR SpectroscopyThe synthetic routes are summarized in Scheme 2. Clearly, the dichloride 4 [11] offers great synthetic potential for further transformations. It proved necessary to use the salt elimination reaction of 4 with dilthium selenide [12] or -telluride [12] to obtain pure samples of 6c and in particular of 6d. In principle, the strained four-membered cycle in 5 [8] appears to be attractive for insertion reactions. [7b] However, it does not react with tellurium, it reacts sluggishly with selenium, and somewhat more readily with sulfur. Surprisingly, 5 does not react with bis(trimethylsilyl)peroxide at room temp., whereas its reaction with trimethylamine N-oxide [13] affords the known disiloxane 6a [9,11,14] quantitatively under mild conditions. Silyl-substituted 1,2-Dicarba-closo-dodecaborane(12) Derivatives Scheme 1. Some known 1,2-silyl-substituted ortho-carborane derivatives, obtained from the reactions of 1,2-dilithio-1,2-dicarba-closo-dodecaborane(12) with various chlorosilanes. Scheme 2. Routes to 1,1,3,3-tetramethyl-4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-disila-2-chalkogena-cyclopentanes 6a-6d.The compounds 6b,c,d are crystalline yellowish (6b, 6c) or yellow (6d) solids sensitive to moisture...

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2,3,4-Tricarba-nido-hexaboranes(7) with a Bridging B−Ethyl−B Moiety

Cited by 9 publications

References 0 publications

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)

Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

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2,3,4-Tricarba-nido-hexaboranes(7) with a Bridging B−Ethyl−B Moiety

Cited by 9 publications

References 0 publications

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Synthesis, spectroscopic characterization, and in vitro biological activity of organotin(IV) complexes of (E)‐3‐(4‐methoxyphenyl)‐2‐phenyl‐2‐propenoic acid

Triel–hydride triel bond between ZX3 (Z = B and Al; X = H and Me) and THMe3 (T = Si, Ge and Sn)

Molecular Structures, Reactivity, and NMR Spectroscopic Studies of Cyclic and Non‐cyclic Silyl‐substituted 1, 2‐Dicarba‐closo‐dodecaborane(12) Derivatives

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Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)