Publisher：American Chemical Society (ACS)  

The synthesis, structure, and properties of a stable, linear 2-stannapropadiene are reported. The identical C=Sn bonds in this 2-stannapropadiene are the shortest hitherto reported C–Sn bonds. This 2-stannapropadiene features a 119Sn NMR signal at 507 ppm for the central tin atom, indicative of an unsaturated SnIV oxidation state. Treatment of this 2-stannapropadiene with SnCl2·dioxane resulted in the formation of a novel four-membered cyclic 1,1-dichloro-1,3-distannetane.

DOI： 10.26434/chemrxiv-2023-2d7rc

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Language：English   Publishing type：Research paper (scientific journal)  

A series of metal-organic frameworks (MOFs) based on zinc ions and two triptycene ligands of different size have been synthesized under solvothermal conditions. Structural analyses revealed that they are isostructural 3D-network MOFs. The high porosity and thermal stability of these MOFs can be attributed to the highly rigid triptycene-based ligands. Their BET specific surface areas depend on the size of the triptycene ligands. In contrast to these surface-area data, the H2 and CO2 adsorption of these MOFs is larger for MOFs with small pores. Consequently, we introduced functional groups to the bridge-head position of the triptycene ligands and investigated their effect on the gas-sorption properties. The results unveiled the role of the functional groups in the specific CO2 binding via an induced interaction between adsorbates and the functional groups. Excellent H2 and CO2 properties in these MOFs were achieved in the absence of open metal sites.

DOI： 10.1002/chem.202302080

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Language：English   Publishing type：Research paper (scientific journal)  

While analogues of allenes with heavier main-group elements (group 14-16) have been extensively studied, 2-heteraallenes are rare chemical species whose properties are mostly unknown. It is also notable that the synthesis and isolation of allene-type molecules are not widespread, despite the extensive study of two-coordinated low-valent chemical species.

DOI： 10.1039/d3dt01559a

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Language：English   Publishing type：Research paper (scientific journal)  

Allenes (>C=C=C<) are classified as cumulated dienes with a linear structure and an sp-hybridized central carbon atom. We have synthesized and isolated a stable 2-germapropadiene with bulky silyl substituents. The 2-germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. An X-ray diffraction electron-density-distribution (EDD) analysis of this 2-germapropadiene confirmed the linear C=Ge=C geometry with a formally sp-hybridized germanium atom that bears two orthogonal C=Ge π-bonds. Based on detailed structural and computational studies, we concluded that the linear geometry of the isolated 2-germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2-germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic.

DOI： 10.1002/anie.202302836

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Language：English   Publishing type：Research paper (scientific journal)  

We have developed highly porous Cu-based metal-organic frameworks (MOFs) using carbazole-type linkers. The novel topological structure of these MOFs was revealed by single-crystal X-ray diffraction analysis. Molecular adsorption/desorption experiments indicated that these MOFs are flexible and change their structure upon adsorption/desorption of organic solvents and gas molecules. These MOFs exhibit unprecedented properties that allow controlling their flexibility by adding a functional group onto the central benzene ring of the organic ligand. For example, the introduction of electron-donating substituents increases the robustness of the resulting MOFs. These MOFs also exhibit flexibility-dependent differences in gas-adsorption and -separation performance. Thus, this study represents the first example of controlling the flexibility of MOFs with the same topological structure via the substituent effect of functional groups introduced into the organic ligand.

DOI： 10.1002/chem.202203442

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane, obtained from the reaction of a bissilylcarbenoid ((R2CBrLi)-C-Si; R-Si=SiMePh2) with elemental selenium, is reported. The molecular structures of these cyclic polyselenides were determined using single-crystal X-ray diffraction analysis. The selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane with triphenylphosphine afforded the corresponding tetraselenolane in quantitative yield. Further deselenation of the tetraselenolane with excess triphenylphosphine did not furnish the expected selenoketone but the diselenirane, as confirmed by spectroscopic analysis.

DOI： 10.1002/ejic.202200780

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A stable dibenzo-1,6,2,5-dioxadisilocine was synthesized as a difunctional electrophile for double-silylation reactions. Its molecular structure was fully characterized by spectroscopic means and single-crystal X-ray diffraction analysis. The reductive coupling with phenanthrene using a dispersion of sodium afforded an unexpected silylated polycyclic compound via a formal [3+3] dimerization of phenanthrene skeletons.

DOI： 10.1246/cl.220478

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Language：Japanese   Publisher：The Society of Synthetic Organic Chemistry, Japan  

Gas storage and separation are closely related to various aspects of human society, such as the alleviation of greenhouse effect, promoting clean energy, and controlling harmful gases. In particular, hydrogen has been enthusiastically researched as a clean energy source that emits no greenhouse gases. Therefore, there are requirements for safe methods to manufacture, store, and transport hydrogen. Conventionally, hydrogen storage materials are metal hydrides and metal amides that react violently with moisture, and their usage environments are limited by the extreme conditions required for hydrogen gas generation. Metal-organic frameworks (PCP/MOFs) are porous coordination materials that are composed of organic ligands and metal ions. Because of their ability to efficiently adsorb small molecules, PCP/MOFs have potential applications in e.g., gas adsorption, catalysis, as well as energy storage and conversion. Functionalization and modification of the organic ligands to construct new MOFs are fascinating and significant areas in crystal engineering owing to the potential applications of the resulting materials. We describe the synthesis and gas-adsorption properties of novel MOFs using the functionalized organic ligands.

DOI： 10.5059/yukigoseikyokaishi.81.46

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Language：English   Publishing type：Research paper (scientific journal)  

Compounds with multiple bonds between elements of the second and fifth periods are extremely unstable, and systematic investigations into their properties remain elusive. Herein, we report a tellurium-centered heteroallene that contains multiple bonds between carbon and tellurium. This compound is the first example of bis(methylene)-λ4-tellane, which was synthesized and fully characterized using multinuclear NMR spectroscopy and X-ray crystallography. In the solid state, this λ4-tellane exhibits a bent allene structure for the C═Te═C moiety and unsaturated Te-C bonds. Interestingly, the allene-type structure is retained in the solution, which is reflected in an absorption band due to the π-π* transition at 610 nm. This λ4-tellane also exhibits unique reactivity toward dihalogermylenes, which yielded rare cyclic telluragermetanes.

DOI： 10.1021/acs.inorgchem.2c02697

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Publishing type：Part of collection (book)   Publisher：Elsevier  

DOI： 10.1016/b978-0-12-818655-8.00033-0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Zinc terephthalate metal-organic framework (MOF) MOF-5 and some of its dialkylated derivatives (R-2-MOF-5; R=Me, Et, Pr, Bu) were obtained from a solvothermal synthesis using 2,5-dialkyl-1,4-benzenedicarboxylic acids with zinc nitrite. The effect of the solvent on the solvothermal synthesis of R-2-MOF-5 was investigated. For R=H and Me, interpenetrating or non-interpenetrating MOFs obtained depending on the choice of reaction solvent, while for R=Et, Pr, and Bu, no such solvent effect was observed, and only jungle-gym-type MOFs were generated. All compounds were fully characterized using powder X-ray diffraction analysis (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). After activation, all these compounds exhibit significant porosity, as confirmed by N-2-, H-2-, and CO2-sorption experiments. The N-2-adsorption capacity of these compounds depends on the size of the attached alkyl groups, while the H-2-uptake values tend to increase for the alkyl-functionalized MOFs relative to the unfunctionalized parent MOFs and exhibit a maximum value for Pr-2-MOF-5.

DOI： 10.1002/ejic.202100466

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Language：Japanese   Publisher：水素エネルギー協会  

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Language：English   Publishing type：Research paper (scientific journal)  

The first example of an interpenetrated methyl-modified MOF-5 with the formula Zn4O(DMBDC)3(DMF)2, where DMBDC2- is 2,5-dimethylbenzene-1,4-dicarboxylate and DMF is N,N-dimethylformamide (henceforth denoted as Me2MOF-5-int), namely, poly[tris(μ4-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-μ4-oxido-tetrazinc(II)], [Zn4(C10H8O4)3O(C3H7NO)2]n, has been obtained from a solvothermal synthesis of 2,5-dimethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2·6H2O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me2MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer-Emmett-Teller surface area of Me2MOF-5-int (660 m2 g-1), determined by N2 adsorption, is much lower than that of nonpenetrated Me2MOF-5 (2420 m2 g-1). However, Me2MOF-5-int displays an H2 uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non-interpenetrated Me2MOF-5 (1.51 wt%).

DOI： 10.1107/S2053229620010177

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Language：English   Publishing type：Research paper (scientific journal)  

Two mixed-ligand metal-organic frameworks, [Zn2(BDHA)0.5(INA)3] (MOF-1: H2BDHA = benzene-1,4-dihydroxamic acid; HINA = isonicotinic acid) and [Co2(BDHA)0.5(INA)3(DMF)] (MOF-2), were solvothermally synthesized and fully characterized by single-crystal X-ray crystallography as well as N2, H2, and CO2 gas-sorption measurements. The results constitute the first detailed analysis of the bonding environment around the hydroxamates in such MOFs, which are simultaneously decorated with Lewis-basic sites from the hydroxamate moieties and metal sites predisposed for coordinative unsaturation. MOF-2 shows a desirably selective adsorption of CO2 relative to N2.

DOI： 10.1039/d0dt01105c

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

The dinuclear (thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes1and2were obtained from the reaction of two equivalents of AuCl(SMe2) with the stable bis(methylene)-lambda(4)-chalcogenanes3and4, respectively. The reaction proceeds under elimination of the chlorosilane moiety of3and4. Complexes1and2were characterized by spectroscopic and X-ray diffraction (XRD) analyses. The(13)C NMR signals for the carbene centers of 1 (309 ppm) and 2 (345 ppm) are by more than 150 ppm downfield shifted relative to those for other known (NHC)AuCl complexes. These results indicate that (chalcogeno)(silyl)carbenes, like (amino)(silyl)carbenes, belong to the push-spectator family of carbenes.

DOI： 10.1039/d0dt00967a

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The dialkylgermylene Trp*Ge-2: (Trp*: peripherally extended sterically demanding alkyl groups based on the triptycyl (Trp) framework), was obtained from the reaction of Trp*Li with GeCl2 center dot dioxane. The structure of Trp*Ge-2: was unequivocally determined by NMR and UV-vis spectroscopy, mass spectrometry, and a single-crystal X-ray diffraction analysis. Moreover, the reactivity of Trp*Ge-2: was examined.

DOI： 10.1246/bcsj.20190338

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Bis(methylene)-lambda(4)-selane 1, which represents a new class of heteroallenes, was synthesized and isolated as a stable purple crystalline solid. X-ray crystallographic analysis revealed a bent allene-type structure with pseudo C-2v symmetry and a bent CSeC moiety that contains a 3-center-4-electron pi-bond. The NMR spectrum of 1 shows compelling evidence for a slow rotation of the SeC moieties at room temperature. The Se-77 NMR spectrum of 1 contains one signal in the region characteristic for Se(iv) compounds.

DOI： 10.1039/c9cc04121d

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Hypervalent tetraaryltellurium(IV) compounds of the type Ar4TeIV (1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar = p-t-BuC6H4; 4: Ar = p-F3CC6H4) were prepared via a convenient one-pot reaction between the isolated corresponding ArLi reagent and TeCl4. X-ray crystallographic analyses of 1-4 revealed distortedpseudo-trigonal-bipyramidal (TBP) structures for Ar 4 Te and the TBP character was analyzed by the dihedral angle method.

DOI： 10.1246/bcsj.20180380

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Publishing type：Part of collection (book)   Publisher：Georg Thieme Verlag  

Abstract

The use of S,S-acetals is increasingly popular as a strategy for the protection of carbonyl groups because, in comparison to the analogous acetals, they are chemically inert under many reaction conditions; this is due to the chemical softness of sulfur atoms. In this context, the deprotection of S,S-acetals to reveal the carbonyl group is of great importance. This update describes methods for the deprotection of S,S-acetals published between 2007 and 2017, and provides an update to Section 30.3.7.

DOI： 10.1055/sos-sd-130-00297

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MDPI  

Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2- (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed isolating stable crystalline organochalcogenyldichlorogermanes.

DOI： 10.3390/inorganics6030068

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Language：English   Publishing type：Research paper (scientific journal)  

A series of Group 2 metal bis(arenecarbochalcogenoato)(crown ether) complexes M(EE'CAr)2(L)(L')x (M = Mg, Ca, Sr, Ba; Ar = aryl; E = S, Se; E' = O, S; L = H2O or THF; L' = 15-crown-5, 18-crown-6) were synthesized and their structures were revealed by X-ray analyses. The two carbothioato ligands in Mg, Ca and Sr 15-crown-5 complexes are located on the same side of the crown ether plane, while those in Mg, Ca, Sr, and Ba 18-crown-6 compounds are on both sides of the 18-crown-6 plane (trans relative to the plane). For the Ca 15-crown-5 complex, both carbothioato ligands are connected to the central Ca ion through an oxygen atom in a monodentate manner, and the two hydrogen atoms of the coordinated water molecule are intramolecularly hydrogen-bonded with thiocarbonyl sulfur atoms. One of the two carbothioate groups in the Ca 18-crown-6 complex is connected in a bidentate manner to the central metal, while the other is connected in a monodentate manner through an oxygen atom. The two thiocarboxylato ligands in the Sr 15-crown-5 congener are connected in a bidentate fashion to the same side of the crown ether plane. The Ca and Sr compounds are the first examples of alkali earth metal carbochalcogenoate complexes in which carbochalcogenolato ligands are connected in a monodentate manner through an oxygen atom. Both chalcogenoato ligands in Ba(SOCC6H4Me-4)2(18-crown-6) and Sr(SeOCC6H4Me-4)2(18-crown-6) are coordinated in a bidentate manner to the central metal ion.

DOI： 10.1039/c8dt01959b

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Language：English   Publishing type：Research paper (scientific journal)  

Bis(methylene)-λ4 -sulfane 1, a >C=S=C< heterocumulene, was obtained as a red crystalline solid from the reaction between elemental sulfur and a carbenoid that contains sterically demanding silylalkyl groups. Under atmospheric conditions, and even at elevated temperatures, 1 exhibits extraordinary stability. The molecular structure and electron-density distribution of 1 were analyzed by single-crystal X-ray diffraction analysis, which revealed a bent C=S=C geometry with C=S=C π-bonds. These results, combined with those of variable-temperature NMR measurements and theoretical calculations suggest a slow rotation of the S=C moieties in 1, the stability and structure of which were further examined by theoretical calculations.

DOI： 10.1002/chem.201800828

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Trp*, a novel triptycene (Trp)-based aliphatic steric protection group was synthesized, and its potential to offer kinetic stabilization by steric protection was evaluated in the context of synthesizing a sulfenic acid (RSOH), i.e., a highly reactive sulfur-containing species. The isolated sulfenic acid Trp* SOH is thermally very stable, which clearly demonstrates the steric protection provided by Trp*.

DOI： 10.1246/cl.171230

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Sulfenyl chlorides, i.e., di-coordinated sulfur(II) chlorides are useful precursors for a variety of organic sulfur compounds. Herein, the synthesis, structure, and reactivity of a sulfenyl chloride that bears a bulky tris(dimethylphenylsilyl) methyl group on the sulfur atom are reported. The thermolysis of this sulfenyl chloride resulted in the generation of the corresponding bissilylthioketone via the 1,2-elimination of chlorodimethyl-phenylsilane.

DOI： 10.1246/cl.170188

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

Stable selenenyl-chlorophosphines, bearing a silylalkyl group, were synthesized. Subsequent treatment with Lewis acids such as AlCl3 afforded the corresponding phospha-alkenes. A reaction mechanism that proceeds through an intramolecular 1,2-elimination of chlorosilane was proposed.

DOI： 10.1002/ejic.201500989

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Language：English   Publishing type：Research paper (scientific journal)  

Reaction of the stable digermyne BbtGe[triple bond, length as m-dash]GeBbt (Bbt = 2,6-[CH(SiMe3)2]2-4-[C(SiMe3)3]-C6H2) with ethylene initially afforded the corresponding 1,2-digermacyclobutene. Depending on the reaction conditions applied, further reaction of this 1,2-digermacyclobutene with ethylene furnished two different reaction products: a 1,4-digermabicyclo[2.2.0]hexane or a bis(germiranyl)ethane. Combined experimental and theoretical results suggested that the 1,4-digermabicyclo[2.2.0]hexane and the bis(germiranyl)ethane are the thermodynamic and kinetic reaction products, respectively. A reaction mechanism in agreement with these results was proposed.

DOI： 10.1039/c5sc01266j

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Language：Japanese   Publisher：SOC SYNTHETIC ORGANIC CHEM JPN  

The organophosphorus radicals have drawn much attention in organic chemistry, biological processes, and functional materials due to their high reactivity Although various species of organophosphorus radicals in solution have been observed by EPR spectroscopy, only a few examples have been isolated in the solid state. By using suitable bulky substituents, isolation of organophosphorus radicals such as dialkylphosphinyl radical, triarylphosphine radical cation, and tetraaryldiphosphine radical cation were achieved. The EPR spectra of those radicals showed the spin density of their radicals are mainly localized on phosphorus atom.

DOI： 10.5059/yukigoseikyokaishi.73.276

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Language：Japanese   Publisher：The Society of Synthetic Organic Chemistry, Japan  

The organophosphorus radicals have drawn much attention in organic chemistry, biological processes, and functional materials due to their high reactivity. Although various species of organophosphorus radicals in solution have been observed by EPR spectroscopy, only a few examples have been isolated in the solid state. By using suitable bulky substituents, isolation of organophosphorus radicals such as dialkylphosphinyl radical, triarylphosphine radical cation, and tetraaryldiphosphine radical cation were achieved. The EPR spectra of those radicals showed the spin density of their radicals are mainly localized on phosphorus atom.

DOI： 10.5059/yukigoseikyokaishi.73.276

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Publisher：Wiley  

DOI： 10.1002/chin.201432205

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A selenium-substituted phosphaalkene, (Me3Si)(2)C=PSeTrp (1, Trp: 9-triptycyl), was synthesized by two methods, substitution reaction of (Me3Si)(2)C=PCl (3) with TrpSeLi, and treatment of TsiP(Cl)SeTrp (4, Tsi: C(SiMe3)(3)) with a catalytic amount of AlCl3. The newly, obtained phosphaalkene was characterized in detail.

DOI： 10.1246/cl.130862

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

We expected that the chemical trapping products of low-coordinated tellurenyl cation species can also be kinetically stabilized by the Tbt or Bbt group. Recently, we have reported the halogenation reactions of Bbt-substituted ditelluride, BbtTeTeBbt, leading to the formation of the Te-II-Te-IV mixed-valent tellurenyl fluoride, BbtTeTe(F)(2)Bbt, and tellurenyl halides, BbtTeX (X = Cl, Br, I). During the dehalogenation reactions of these tellurium halides, it is rational to postulate the formation of a tellurenyl cation species as an intermediate. In this paper, we report the successful trapping of tellurenyl cation species with butadienes or triphenylphosphane, and the regeneration of the tellurenyl cation species by thermal retro [1+4] cycloaddition of the diene adducts.

DOI： 10.1002/ejic.201101313

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Language：English   Publishing type：Research paper (scientific journal)  

DOI： 10.1002/asia.201100368

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

Halogenation reactions of BbtTe-TeBbt (Bbt; 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris (trimethylsilyl)methyl]phenyl) with SO2Cl2, Br-2, and I-2 were examined. When 1 equiv of the reagents were used, the corresponding tellurium monohalides were obtained as stable crystalline compounds. Although iodination reaction of BbtTe-TeBbt using 3 equiv of I-2 afforded BbtTeI, treatment of BbtTe-TeBbt with 3 equiv of SO2Cl2 and Br-2 gave the corresponding tellurium trthalides, BbtTeX(3)(X = Cl, Br), as stable crystalline compounds. Characterization of the obtained tellurium mono- and trihalides was achieved by the spectroscopic and crystallographic analyses, together with theoretical calculations. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:405-411, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20698

DOI： 10.1002/hc.20698

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