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1.
Chem Asian J ; 19(11): e202400168, 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38578726

RESUMO

Controlled insertion into a single P-P bond of white phosphorus (P4) was achieved by employing a diaryl stabilized stannylene, Ar*2Sn (Ar*=2,6-bis(benzhydryl)-4-iPr-phenyl). Conversions of the stannylene with P4 gave a non-pyrophoric, air-stable storage compound, which releases P4 quantitively upon irradiation with light (354 or 455 nm). Alternatively, the phosphorus cage is detached by reacting the storage compound with PhChChPh (Ch=Se, Te). Despite the recent advances in the directed conversion of P4 using main group element compounds, Ar*2Sn constitutes only the second structurally characterized example of a stannylene capable of performing controlled, reversible addition and release of white phosphorus.

2.
Ophthalmol Ther ; 12(4): 2087-2101, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37211587

RESUMO

INTRODUCTION: Intraocular lenses (IOL) should remain in the eye for life after implantation into the capsular bag during cataract surgery. The material must meet various requirements. It is crucial that the material has the best biocompatibility, and it should be flexible and soft for best possible implantation process but also sufficiently stable and stiff for good centering in the eye and posterior capsule opacification prevention. METHODS: In this laboratory experiment, we used nano-indentation for the mechanical assessment of three hydrophobic acrylic (A, B, C), three hydrophilic acrylic (D, E, F), and one silicone (G) intraocular lens. We wanted to determine whether some react more sensitively to touching/handling than others. The indentation elastic modulus and the creep were obtained from the force displacement curve. For measuring penetration depth and testing of possible damage to the intraocular lenses, the samples were measured at room temperature. A 200-µm-diameter ruby spherical tipped indenter was used for all the tests. Indentations were made to three different maximum loads, namely 5 mN (milli Newton), 15 mN, and 30 mN and repeated three times. RESULTS: The lowest penetration depth (12 µm) was observed with IOL B. However, IOL A, D, and F showed similar low penetration depths (20, 18, and 23 µm, respectively). Lenses C and E showed slightly higher penetration depths of 36 and 39 µm, respectively. The silicone lens (G) showed the greatest penetration depth of 54.6 µm at a maximum load of 5 mN. With higher maximal loads (15 and 30 mN) the penetration depth increased significantly. Lens C, however, showed the same results at both 15 and 30 mN with no increase of penetration depth. This seems to fit well with the material and manufacturing process of the lens (lathe-cut). During the holding time of 30 s at constant force all six acrylic lenses showed a significant increase of the creep (CIT 21-43%). Lens G showed the smallest creep with 14%. The mean indentation modulus (EIT) values ranged from 1 to 37 MPa. IOL B had the largest EIT of 37 MPa, which could be caused by the low water content. CONCLUSION: It was found that results correlate very well with the water content of the material in the first place. The manufacturing process (molded versus lathe-cut) seems to play another important role. Since all included acrylic lenses are very similar, it was not surprising that the measured differences are marginal. Even though hydrophobic materials with lower water content showed higher relative stiffness, penetration and defects can also occur with these. The surgeon and scrub nurse should always be aware that macroscopic changes are difficult to detect but that defects could theoretically lead to clinical effects. The principle of not touching the center of the IOL optic at any time should be taken seriously.

3.
Organometallics ; 41(23): 3686-3696, 2022 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-36533114

RESUMO

In continuation of our recent studies on group 14 rings with exocyclic silicon-carbon double bonds, we report here on the synthesis and reactivity of previously unknown acyl-substituted 1,4-disilacyclohexa-2,5-dienes. 1,1,4,4-Tetrakistrimethylsilyl-1,4-disilacyclohexa-2,5-diene 1 cleanly afforded the silyl anion 1-K after addition of 1 equiv of KO t Bu. 1-K subsequently could be reacted with various electrophiles to the expected substitution products including compounds 4 and 5. When photolyzed with λ > 300 nm radiation, 4 and 5 undergo Brook-type 1,3-Si → O migration reactions to generate the corresponding 1,4-disilacyclohexadienes with exocyclic Si=C bonds as the primary products. These metastable silenes only could be characterized in form of appropriate quenching products. The reaction of compound 4 with KO t Bu followed by the addition of 1 equiv of PhMe2SiCl surprisingly gave the silylated 1,4-disilanorbornadiene cages 8 and 9 instead of the expected exocyclic silene. The responsible sila-Peterson-type mechanism could be elucidated by density functional theory calculations at the conductor-like polarizable continuum model (THF) B3LYP-GD3/6-31 + G(d) level and by the isolation and characterization of unstable intermediate products after proper derivatization.

4.
Chemistry ; 28(23): e202200276, 2022 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-35218252

RESUMO

A series of non-fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki-coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X-ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB-T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure-property relationships of perylene-linker-perylene compounds.

5.
Chem Commun (Camb) ; 57(78): 10095-10098, 2021 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-34518844

RESUMO

From conversions of Ar2SnH2 (Ar = Tripp, Dipp; Tripp = 2,4,6-Triisopropylphenyl, Dipp = 2,6-Diisopropylphenyl), and a bismuth(III) amide, Bi[N(SiMe3)2]3, we isolated the first representatives of mixed, uncharged Bi/Sn clusters, Bi8Sn3Ar6. Along with unprecedented bicyclo[2.2.0]hexanes, (HAr2Sn)2Sn2Bi4, these have been characterized by single crystal X-Ray diffraction, heteronuclear NMR, vibrational and UV-Vis spectroscopy. Quantum-chemical calculations were carried out in order to understand bonding within the isolated polyhedral compounds.

6.
Chem Commun (Camb) ; 56(3): 336-339, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31808473

RESUMO

The reaction of diphenyltin dihydride with LiAlH4 gives access to a set of charged tin cages as their lithium salts. Variation in the ratio of reactants provides a perstannabicyclooctane dianion and a perstannanorbornane as the di- and monoanions. These compounds can be synthesised selectively by careful stoichiometric control and have been characterised by single crystal X-ray diffractometry, NMR and UV-vis spectroscopy. Computational exploration of the electronic structures of these compounds was undertaken and, in agreement with structural and spectroscopic features, indicated significant σ-delocalisation in the tin skeletons.

7.
Angew Chem Int Ed Engl ; 56(28): 8089-8093, 2017 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-28481426

RESUMO

Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon-carbon bond-forming strategy.

8.
Organometallics ; 33(21): 5956-5959, 2014 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-25400314

RESUMO

The first silenolates with exocyclic structures [(Me3Si)2Si(Si2Me4)2SiC(R)O]-K+ (2a: R = 1-adamantyl; 2b: mesityl; 2c: o-tolyl) were synthesized by the reaction of the corresponding acylcyclohexasilanes 1a-c with KOtBu. NMR spectroscopy and single-crystal X-ray diffraction analysis suggest that the aryl-substituted silenolates 2b,c exhibit increased character of functionalized silenes as compared to the alkyl-substituted derivative 2a due to the different coordination of the K+ counterion to the SiC(R)O moiety. 2b,c, thus, reacted with ClSiiPr3 to give the exocyclic silenes (Me3Si)2Si(Si2Me4)2Si=C(OSiiPr3)R (3b: R = Mes; 3c: o-Tol), while 2a afforded the Si-silylated acylcyclohexasilane 1d. The thermally remarkably stable compound 3b, which is the first isolated silene with the sp2 silicon atom incorporated into a cyclopolysilane framework, could be fully characterized structurally and spectroscopically.

9.
PLoS One ; 8(4): e59797, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-23565169

RESUMO

The control of protein aggregation is an important requirement in the development of bio-pharmaceutical formulations. Here a simple protein model is proposed that was used in molecular dynamics simulations to obtain a quantitative assessment of the relative contributions of proteins' net-charges, dipole-moments, and the size of hydrophobic or charged surface patches to their colloidal interactions. The results demonstrate that the strength of these interactions correlate with net-charge and dipole moment. Variation of both these descriptors within ranges typical for globular proteins have a comparable effect. By comparison no clear trends can be observed upon varying the size of hydrophobic or charged patches while keeping the other parameters constant. The results are discussed in the context of experimental literature data on protein aggregation. They provide a clear guide line for the development of improved algorithms for the prediction of aggregation propensities.


Assuntos
Simulação de Dinâmica Molecular , Proteínas/química , Algoritmos , Coloides , Interações Hidrofóbicas e Hidrofílicas , Solubilidade , Eletricidade Estática
10.
Chemistry ; 19(46): 15504-17, 2013 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-24591247

RESUMO

Stabilization of the central atom in an oxidation state of zero through coordination of neutral ligands is a common bonding motif in transition-metal chemistry. However, the stabilization of main-group elements in an oxidation state of zero by neutral ligands is rare. Herein, we report that the transamination reaction of the DAMPY ligand system (DAMPY=2,6-[ArNH-CH2 ]2 (NC5 H3 ) (Ar=C6 H3 -2,6-iPr2 )) with Sn[N(SiMe3 )2 ]2 produces the DIMPYSn complex (DIMPY=(2,6-[ArNCH]2 (NC5 H3 )) with the Sn atom in a formal oxidation state of zero. This is the first example of a tin compound stabilized in a formal oxidation state of zero by only one donor molecule. Furthermore, three related low-valent Sn(II) complexes, including a [DIMPYSn(II) Cl](+) [SnCl3 ](-) ion pair, a bisstannylene DAMPY{Sn(II) [N(SiMe3 )2 ]2 }2 , and the enamine complex MeDIMPYSn(II) , were isolated. Experimental results and the conclusions drawn are also supported by theoretical studies at the density functional level of theory and (119) Sn Mössbauer spectroscopy.

11.
J Am Chem Soc ; 131(43): 15952-62, 2009 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-19799427

RESUMO

Reactions of 1,2-dipotassiotetrakis(trimethylsilyl)disilane with group 4 metallocene dichlorides lead to the formation of the respective metallocene 1,1,2,2-tetrakis(trimethylsilyl)disilene complexes. While the disilene titanocene complex could be structurally characterized, the zirconocene and hafnocene compounds, which are believed to possess some degree of bis-[bis(trimethylsilyl)silylene] character, can only be isolated in substance as the respective trimethylphosphane adducts. Analogous metallocene 1,1,2,2-tetrakis(trimethylsilyl)digermene complexes and a tetrakis(trimethylsilyl)silagermene complex were prepared. Instead of metallocene 1,1,2,2-tetrakis(trimethylsilyl)distannene complexes, four-membered rings composed of a metallocene and three bis(trimethylsilyl)stannylene units were obtained.

12.
J Am Chem Soc ; 130(51): 17460-70, 2008 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-19053480

RESUMO

Reactions of trisilylated silylfluorides with potassium tert-butoxide were found to give disilylated fluorosilylenoids. The latter undergo a self-condensation reaction, leading to the formation of beta-fluorodisilanyl anions, which may also be considered as fluoride adducts of disilenes. The stereochemical outcome of this self-condensation depends on the bulkiness of the silyl substituents. Thus, mixtures of diastereomers are obtained in some cases. Reaction of a disilene adduct with magnesium bromide triggers metal fluoride elimination and formation of the respective tetrasilylated disilene. Attempts to exchange one silyl group of the starting material for a methyl, phenyl, or tert-butyl group led to a different course of reaction for the methyl and phenyl cases. The tert-butyl-substituted example gave the expected disilene adduct, but it was not the main product.

13.
Magn Reson Chem ; 46(9): 865-71, 2008 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-18613256

RESUMO

(13)C shifts of disubstituted cyclopentane and cyclohexane derivatives were compared in dependence on the relative configuration of the two substituents. A diequatorial substitution correlates with deshielding compared to other substitution patterns. Some novel fluorinated cyclopentanes and -hexanes including their DFT calculation-assisted structure elucidation are described.


Assuntos
Cicloexanos/química , Ciclopentanos/química , Espectroscopia de Ressonância Magnética/métodos , Espectroscopia de Ressonância Magnética/normas , Isótopos de Carbono , Simulação por Computador , Cicloexanos/síntese química , Ciclopentanos/síntese química , Modelos Químicos , Estrutura Molecular , Padrões de Referência , Estereoisomerismo
14.
Inorg Chem ; 47(8): 3023-33, 2008 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-18345620

RESUMO

Ab initio calculations were carried out to investigate the potential-energy surface for internal rotation of the methylated digermanes hexamethyldigermane Me(3)GeGeMe(3) ( 1), dichlorotetramethyldigermane Me(2)ClGeGeClMe(2) ( 2), and tetramethyldigermane Me(2)HGeGeHMe(2) ( 3). Different basis sets [6-31+G(d), SDD, aug-cc-pVTZ] were employed at the DFT and MP2 levels of theory to optimize structures and to calculate energies and vibrational frequencies. For 1, one minimum representing a staggered structure was located on the potential-energy surface. For 2 and 3, antiperiplanar conformations with C 2 symmetry were found to be the global minima. Additionally, synclinal minima were located for 2 and 3 when certain basis sets were employed. Determination of structural parameters in the gas phase by gas electron diffraction confirmed the computed predictions for all three compounds. For 2 and 3, the ratios of antiperiplanar to synclinal conformer were detected to be 90:10 (328 K) and 72:28 (293 K), respectively, by gas electron diffraction. The experimentally determined GeGe bond lengths in 1, 2, and 3 in the gas phase are 241.4(1), 242.7(2) (averaged for antiperiplanar and synclinal), and 241.7(1) pm (equal for antiperiplanar and synclinal). Only averaged structures were observed, using Raman spectroscopy, for 2 and 3 because the wavenumber differences are small between conformers and there is only a small contribution from the second conformer in each case. For 2, the crystal structure was also determined by X-ray diffraction. An anticlinal structure (with Cl atoms eclipsing the C atoms) was found with a GeGe bond length of 242.1 pm.

15.
Chemphyschem ; 8(5): 735-44, 2007 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-17335111

RESUMO

The conformers of the monohalocyclohexasilanes, Si(6)H(11)X (X=F, Cl, Br or I) and the haloundecamethylcyclohexasilanes, Si(6)Me(11)X (X=F, Cl, Br or I) are investigated by DFT calculations employing the B3LYP density functional and 6-31+G* basis sets for elements up to the third row, and SDD basis sets for heavier elements. Five minima are found for Si(6)H(11)X-the axial and equatorial chair conformers, with the substituent X either in an axial or equatorial position-and another three twisted structures. The equatorial chair conformer is the global minimum for the X=Cl, Br and I, the axial chair for X=F. The barrier for the ring inversion is approximately 13 kJ mol(-1) for all four compounds. Five minima closely related to those of Si(6)H(11)X are found for Si(6)Me(11)X. Again, the equatorial chair is the global minimum for X=Cl, Br and I, and the axial chair for X=F. Additionally, two symmetrical boat conformers are found as local minima on the potential energy surfaces for X=F, Cl and Br, but not for X=I. The barrier for the ring inversion is approximately 14-16 kJ mol(-1) for all compounds. The conformational equilibria for Si(6)Me(11)X in toluene solution are investigated using temperature dependent Raman spectroscopy. The wavenumber range of the stretching vibrations of the heavy atoms X and Si from 270-370 cm(-1) is analyzed. Using the van't Hoff relationship, the enthalpy differences between axial and equatorial chair conformers (H(ax-)H(eq.)) are 1.1 kJ mol(-1) for X=F, and 1.8 to 2.8 kJ mol(-1) for X=Cl, Br and I. Due to rapid interconversion, only a single Raman band originating from the "averaged" twist and boat conformers could be observed. Generally, reasonable agreement between the calculated relative energies and the experimentally determined values is found.

16.
Chemphyschem ; 7(2): 421-9, 2006 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-16411262

RESUMO

The conformations of dodecamethylcyclohexasilane Si6Me12 and undecamethylcyclohexasilane Si6Me11H have been investigated by ab initio calculations employing the B3LYP density functional with a 6-31+G(d) basis set. Local minima as well as transition structures were calculated with imposed symmetry constraints. For Si6Me12, three unique minima, which correspond to the chair, twist and boat conformations were located with relative zero-point-vibration-corrected energies of 0.0, 7.8 and 11.4 kJ mol(-1). A half-chair conformation with four coplanar silicon atoms connects the chair and twisted minima via an energy barrier of 16.0 and 8.2 kJ mol(-1), respectively. A second transition structure with a barrier of 3.9/0.3 kJ mol(-1) connects the twist with the boat structure. Solution Raman spectra of Si6(CH3)12 and Si6(CD3)12 fully corroborate these results. Below -40 degrees C, the symmetric SiSi ring breathing vibration is a single line, which develops a shoulder (originating from the twist conformer) at longer wavelengths whose intensity increases with increasing temperature. From a Van't Hoff plot, the chair/twist enthalpy difference is 6.6+/-1.5 kJ mol(-1) for Si6(CH3)12 and 6.0+/-1.5 kJ mol(-1) for Si6(CD3)12, which is in reasonable agreement with the ab initio results. Due to the low barrier, the boat conformation cannot be observed, because either the lowest torsional vibration level lies above it or a rapid interconversion between the twist and boat conformations occurs, resulting in averaged Raman spectra. For Si6Me11H, six local minima were located. The chair with the hydrogen atom in the axial position (axial chair) is the global minimum, followed by the equatorial chair (+1.9 kJ mol(-1)) and the three twist conformers (+5.3, +8.0 and +8.1 kJ mol(-1)). The highest local minimum (+11.9 kJ mol(-1)) is a C(s) symmetric boat with the hydrogen atom in the equatorial position. Two possible pathways for the chair-to-chair interconversion with barriers of 13.9 and 14.5 kJ mol(-1) have been investigated. The solution Raman spectra in the SiSi ring breathing region clearly show that below -50 degrees C only the axial and equatorial chairs are present, with an experimental deltaH-value of 0.46 kJ mol(-1). With increasing temperature a shoulder develops which is attributed to the combined twist conformers. The experimental deltaH-value is 6.9 kJ mol(-1), in good agreement with the ab initio results. Due to the low interconversion barriers, the various twist conformers cannot be detected separately.

17.
Chemistry ; 11(16): 4635-42, 2005 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-15959860

RESUMO

Geometry optimizations at the B3LYP/6-31 + G(d) level for a set of X(SiH3)MeSiLi molecules (X = F, OH, NH2, Cl, SH, and PH2) show that the tetrahedral structure prevails in polar solutions; however, it readily isomerizes into a silylenoid with energy barriers of less than 15 kJ mol(-1). Inverted structures, which predominate in the gas phase, could not be located in solution. Configuration inversion is unfavorable, with energy barriers between 80 and 220 kJ mol(-1). The alpha elimination into a silylene moiety and the corresponding LiX is only likely to occur in solution, particularly for X = Cl and SH.

18.
J Am Chem Soc ; 127(1): 70-1, 2005 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-15631453

RESUMO

Reaction of the magnesium transmetalation product of a 1,2-dipotassiodisilane with hafnocene dichloride gives a disilene hafnocene complex. X-ray crystallography of the respective trimethylphosphane adduct provides structural proof for this assignment.

19.
Chemistry ; 9(14): 3320-3, 2003 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-12866076

RESUMO

The first halosilylene stable in solution was investigated by ab initio/NMR calculations (IGLO SOS-DFPT PW91/B2//B3LYP/6-31+G(d)). The delta (29)Si(calc) of (Me(3)Si)(3)CSiBr (446 ppm) does not agree with the measured NMR signal at 106 ppm assigned to the free halosilylene. From the possible silylene complexes in the reaction solution, two structures agree with the observed NMR signal: the (Me(3)Si)(3)CSiBr(2) anion (delta (29)Si(calc)=124 ppm) and the unsolvated and solvated complex of the anion with two Li(+) (delta (29)Si(calc)=117 and estimated 134 ppm). Additionally the delta (29)Si(calc) of alkylsilylenes, R-Si-X, ranging from 200 to 900 ppm are presented to guide NMR identification in future silylene synthesis.

20.
Chemistry ; 8(5): 1024-30, 2002 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-11891888

RESUMO

Alpha-substituent effects on inversion barriers and NMR chemical shifts have been studied on a set of silyl anions, [X(3-n)Y(n)Si](-) (X, Y=H, CH(3), and SiH(3)). The MP2/6-31+G* optimized structures show a pattern of increasing inversion barriers with augmenting numbers of methyl substituents. The highest barrier of 48.5 kcalmol(-1) is obtained for the (CH(3))(3)Si(-) ion. The silyl group displays the opposite effect by decreasing the inversion barrier to a minimum of 16.3 kcalmol(-1) in (SiH(3))(3)Si(-). The influence of counterions on these barriers is probed by addition of a lithium or potassium cation. In most cases, a decrease of the energy barriers with respect to the bare anions is observed. The (29)Si NMR chemical shifts calculated at the IGLO-DFT and GIAO-MP2 level of theory are also analyzed in view of the substituents and counterions.

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