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1.
Dr. María Guadalupe Vasquez-Ríos Dr. Gonzalo Campillo-Alvarado Dr. Dale C. Swenson Prof. Herbert Höpfl Prof. Leonard R. MacGillivray 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(25):e202104604
Cocrystallizations of diboronic acids [1,3-benzenediboronic acid (1,3-bdba), 1,4-benzenediboronic acid (1,4-bdba) and 4,4’-biphenyldiboronic acid (4,4’-bphdba)] and bipyridines [1,2-bis(4-pyridyl)ethylene (bpe) and 1,2-bis(4-pyridyl)ethane (bpeta)] generated the hydrogen-bonded 1 : 2 cocrystals [(1,4-bdba)(bpe)2] (1), [(1,4-bdba)(bpeta)2] (2), [(1,3-bdba)(bpe)2(H2O)2] (3) and [(1,3-bdba)(bpeta)2(H2O)] (4), wherein 1,3-bdba involved hydrated assemblies. The linear extended 4,4’-bphdba exhibited the formation of 1 : 1 cocrystals [(4,4'-bphdba)(bpe)] (5) and [(4,4'-bphdba-me)(bpeta)] (6). For 6, a hemiester was generated by an in-situ linker transformation. Single-crystal X-ray diffraction revealed all structures to be sustained by B(O)−H⋅⋅⋅N, B(O)−H⋅⋅⋅O, Ow−H⋅⋅⋅O, Ow−H⋅⋅⋅N, C−H⋅⋅⋅O, C−H⋅⋅⋅N, π⋅⋅⋅π, and C−H⋅⋅⋅π interactions. The cocrystals comprise 1D, 2D, and 3D hydrogen-bonded frameworks with components that display reactivities upon cocrystal formation and within the solids. In 1 and 3, the C=C bonds of the bpe molecules undergo a [2+2] photodimerization. UV radiation of each compound resulted in quantitative conversion of bpe into cyclobutane tpcb. The reactivity involving 1 occurred via 1D-to-2D single-crystal-to-single-crystal (SCSC) transformation. Our work supports the feasibility of the diboronic acids as formidable structural and reactivity building blocks for cocrystal construction. 相似文献
2.
Jarno Riefer Ludwig Zapf Dr. Raphael Wirthensohn Dr. Philipp T. Hennig Dr. Tatjana Ribbeck Dr. Jan A. P. Sprenger Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《European journal of organic chemistry》2023,26(17):e202300031
Cyanoborane adducts of the Lewis acids B(CN)3, BF(CN)2, and BH(CN)2 with pyridine and 4-cyanopyridine have been obtained in high yields. The syntheses were accomplished by oxidation of the readily available potassium salts of the cyano(hydrido)borate anions [BH(CN)3]− ( MHB ), [BFH(CN)2]− ( FHB ), and [BH2(CN)2]− ( DHB ) with bromine in the presence of the respective pyridine derivative C5H5N or 4-CN-C5H4N as starting material. All six cyanoborane adducts have been characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The reduction of the cyanoborane adducts has been investigated by cyclic voltammetry and the Lewis acidity of the different cyanoboranes has been assessed using the Gutmann-Beckett method. Selected experimental data and trends are compared to theoretical ones, for example fluoride ion affinities (FIAs). 相似文献
3.
《Journal of organometallic chemistry》1991,412(3):C37-C39
Single addition of the nucleophiles X− (X = H, CN, OH) to the less sterically hindered ring in [(η6-C6Me6)Ru(η6-C16H16)][BF4]2 (1) proceeds smoothly to produce, as the sole product, [(exo-η5-C6Me6X)Ru(η6-C16H16)][BF4]. Use of Na[BD4] in place of Na[BH4] gives the expected shift in ν(C-Hexo) in the infrared spectrum. 相似文献
4.
Lisa A. Bischoff Dr. Michael Drisch Dr. Christoph Kerpen Philipp T. Hennig Dr. Johannes Landmann Dr. Jan A. P. Sprenger Dr. Rüdiger Bertermann Dr. Matthias Grüne Qinqin Yuan Dr. Jonas Warneke Dr. Xue-Bin Wang Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(14):3560-3574
High-yield syntheses up to molar scales for salts of [BH(CN)3]− ( 2 ) and [BH2(CN)2]− ( 3 ) starting from commercially available Na[BH4] (Na 5 ), Na[BH3(CN)] (Na 4 ), BCl3, (CH3)3SiCN, and KCN were developed. Direct conversion of Na 5 into K 2 was accomplished with (CH3)3SiCN and (CH3)3SiCl as a catalyst in an autoclave. Alternatively, Na 5 is converted into Na[BH{OC(O)R}3] (R=alkyl) that is more reactive towards (CH3)3SiCN and thus provides an easy access to salts of 2 . Some reaction intermediates were identified, for example, Na[BH(CN){OC(O)Et}2] (Na 7 b ) and Na[BH(CN)2{OC(O)Et}] (Na 8 b ). A third entry to 2 and 3 uses ether adducts of BHCl2 or BH2Cl such as the commercial 1,4-dioxane adducts that react with KCN and (CH3)3SiCN. Alkali metal salts of 2 and 3 are convenient starting materials for organic salts, especially for low viscosity ionic liquids (ILs). [EMIm] 3 has the lowest viscosity and highest conductivity with 10.2 mPa s and 32.6 mS cm−1 at 20 °C known for non-protic ILs. The ILs are thermally, chemically, and electrochemically robust. These properties are crucial for applications in electrochemical devices, for example, dye-sensitized solar cells (Grätzel cells). 相似文献
5.
Yang-Lin Shen Dr. Jun-Ling Jin Dr. Guang-Xiong Duan Peng-Yuan Yu Prof. Yun-Peng Xie Prof. Xing Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):1122-1126
Four silver thiolate clusters, [H3O][(Ag3S3)(BF4)@Ag27(tBuS)18(hfac)6H2O] ⋅ H2O ( 1 ; hfac = hexafluoroacetylacetone), [(Ag3S3)(CF3CO2)@Ag30(tBuS)16(CF3CO2)9(CH3CN)4] ⋅ CF3CO2 ⋅ 4 CH3CN ( 2 ), [(Ag3S3)(MoO4)@Ag30(tBuS)16(CF3CO2)9(CH3CN)4] ⋅ 2 CH3CN ( 3 ), and [(Ag3S3)(CrO4)@Ag30(tBuS)16(CF3CO2)9(CH3CN)4] ⋅ 4 CH3CN ( 4 ), were isolated. They have similar nestlike structures assembled by an [Ag3S3]3− template together with one of the BF4−, CF3CO2−, MoO42−, or CrO42− anions. Interestingly, the solid-state emissions of 2 – 4 are dependent on the templating anions and are tunable from green to orange and then to red by changing the template from CF3CO2− to MoO42− and to CrO42−, and this may be correlated to the charge transfer between these templates to metal atoms. This work helps to understand the templating role of heteroanions and the relationship between structure and properties. 相似文献
6.
《Angewandte Chemie (International ed. in English)》2017,56(10):2795-2799
The first deprotonation of a borohydride anion was achieved by treatment of [BH(CN)3]− with strong non‐nucleophilic bases, which resulted in the formation of alkali‐metal salts of the tricyanoborate dianion B(CN)32− in up to 97 % yield and 99.5 % purity. [BH(CN)3]− is less acidic than (Me3Si)2NH but a stronger acid than i Pr2NH. Less sterically hindered, more nucleophilic bases such as PhLi and MeLi mostly attack a CN group under formation of imine dianions [RC(N)B(CN)3]2−, which can be hydrolyzed to ketones of the [RC(O)B(CN)3]− type. The boron‐centered nucleophile B(CN)32− reacts with CO2 and CN+ reagents to give salts of the [B(CN)3CO2]2− dianion and the tetracyanoborate anion [B(CN)4]−, respectively, in excellent yields. 相似文献
7.
Werner Massa Juraj Kuchr Juraj ernk 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):m337-m339
The title compound, [Ni(C2H8N2)3]6[Cu(CN)3][Cu2(CN)7]2·9H2O, was formed upon dissolution of a freshly prepared precipitate of CuNi(CN)4 in ethylenediamine (en) as a result of complex redox and complexation equilibriums in the presence of air. The compound exhibits an ionic structure and contains three crystallographically independent chiral [Ni(en)3]2+ cations, planar [Cu(CN)3]2− and chiral [(NC)3Cu–(μ‐CN)–Cu(CN)3]5− anions, and water molecules of crystallization. All metal atoms are situated on special positions. One of the Ni atoms lies on a twofold axis, whereas all other metal atoms are located on threefold axes. 相似文献
8.
Dr. Michael Drisch Lisa A. Bischoff Dr. Jan A. P. Sprenger Dr. Philipp T. Hennig Raphael Wirthensohn Dr. Johannes Landmann Dr. Szymon Z. Konieczka Dr. Michael Hailmann Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11625-11633
Different types of high-yield, easily scalable syntheses for cyano(fluoro)borates Kt[BFn(CN)4−n] (n=0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal-free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN)2{OC(O)Et}]− to result in [BF(CN)2{OC(O)Et}]− is described. 相似文献
9.
Johannes Landmann Jan A. P. Sprenger Michael Hailmann Vera Bernhardt‐Pitchougina Helge Willner Nikolai Ignat'ev Eduard Bernhardt Maik Finze 《Angewandte Chemie (International ed. in English)》2015,54(38):11259-11264
Diborane(6) dianions with substituents that are bonded to boron via carbon are very reactive and therefore only a few examples are known. Diborane(6) derivatives are the simplest catenated boron compounds with an electron‐precise B–B σ‐bond that are of fundamental interest and of relevance for material applications. The homoleptic hexacyanodiborane(6) dianion [B2(CN)6]2− that is chemically very robust is reported. The dianion is air‐stable and resistant against boiling water and anhydrous hydrogen fluoride. Its salts are thermally highly stable, for example, decomposition of (H3O)2[B2(CN)6] starts at 200 °C. The [B2(CN)6]2− dianion is readily accessible starting from 1) B(CN)32− and an oxidant, 2) [BF(CN)3]− and a reductant, or 3) by the reaction of B(CN)32− with [BHal(CN)3]− (Hal=F, Br). The latter reaction was found to proceed via a triply negatively charged transition state according to an SN2 mechanism. 相似文献
10.
K. Geetharani Shubhankar Kumar Bose Babu Varghese Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(37):11357-11366
Reaction of [1,2‐(Cp*RuH)2B3H7] ( 1 ; Cp*=η5‐C5Me5) with [Mo(CO)3(CH3CN)3] yielded arachno‐[(Cp*RuCO)2B2H6] ( 2 ), which exhibits a butterfly structure, reminiscent of 7 sep B4H10. Compound 2 was found to be a very good precursor for the generation of bridged borylene species. Mild pyrolysis of 2 with [Fe2(CO)9] yielded a triply bridged heterotrinuclear borylene complex [(μ3‐BH)(Cp*RuCO)2(μ‐CO){Fe(CO)3}] ( 3 ) and bis‐borylene complexes [{(μ3‐BH)(Cp*Ru)(μ‐CO)}2Fe2(CO)5] ( 4 ) and [{(μ3‐BH)(Cp*Ru)Fe(CO)3}2(μ‐CO)] ( 5 ). In a similar fashion, pyrolysis of 2 with [Mn2(CO)10] permits the isolation of μ3‐borylene complex [(μ3‐BH)(Cp*RuCO)2(μ‐H)(μ‐CO){Mn(CO)3}] ( 6 ). Both compounds 3 and 6 have a trigonal‐pyramidal geometry with the μ3‐BH ligand occupying the apical vertex, whereas 4 and 5 can be viewed as bicapped tetrahedra, with two μ3‐borylene ligands occupying the capping position. The synthesis of tantalum borylene complex [(μ3‐BH)(Cp*TaCO)2(μ‐CO){Fe(CO)3}] ( 7 ) was achieved by the reaction of [(Cp*Ta)2B4H8(μ‐BH4)] at ambient temperature with [Fe2(CO)9]. Compounds 2 – 7 have been isolated in modest yield as yellow to red crystalline solids. All the new compounds have been characterized in solution by mass spectrometry; IR spectroscopy; and 1H, 11B, and 13C NMR spectroscopy and the structural types were unequivocally established by crystallographic analysis of 2 – 6 . 相似文献
11.
《Polyhedron》1999,18(26):3527-3531
The redox reaction between [Pt(NH3)4]2+ and [W(CN)8]3− in the presence of Cl− anions in aqueous solution affords single crystals of [PtII(NH3)4]2[WIV(CN)8] and [PtIV(NH3)4Cl2]Cl2. Trapped cyano ligands of [W(CN)8]4− rectangular antiprisms of D2 point symmetry between parallel Pt(II) square planes show that the inner-sphere redox pathway is prohibited. The presence of Cl− counterions enables the formation of [Pt(NH3)4Cl2]Cl2 as the product of the rare outer-sphere pathway of the oxidation of Pt(II) by [W(CN)8]3−. 相似文献
12.
Dr. Vladimir A. Dodonov Weixing Chen Prof. Dr. Yanxia Zhao Prof. Dr. Alexandra A. Skatova Prof. Dr. Peter W. Roesky Prof. Dr. Biao Wu Prof. Dr. Xiao-Juan Yang Prof. Dr. Igor L. Fedushkin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8259-8267
Digallane [L1Ga−GaL1] ( 1 , L1=dpp-bian=1,2-[(2,6-iPr2C6H3)NC]2C12H6) reacts with RN=C=O (R=Ph or Tos) by [2+4] cycloaddition of the isocyanate C=N bonds across both of its C=C−N−Ga fragments to afford [L1(O=C−NR)Ga−Ga(RN−C=O)L1] (R=Ph, 3 ; R=Tos, 4 ). The reactions with both isocyanates result in new C−C and N−Ga single bonds. In the case of allyl isocyanate, the [2+4] cycloaddition across one C=C−N−Ga fragment of 1 is accompanied by insertion of a second allyl isocyanate molecule into the Ga−N bond of the same fragment to afford compound [L1Ga−Ga(AllN− C=O)2L1] ( 5 ) (All=allyl). In the presence of Na metal, the related digallane [L2Ga−GaL2] ( 2 ; L2=dpp-dad=[(2,6-iPr2C6H3)NC(CH3)]2) is converted into the gallium(I) carbene analogue [L2Ga:]− ( 2 A ), which undergoes a variety of reactions with isocyanate substrates. These include the cycloaddition of ethyl isocyanate to 2 A affording [Na2(THF)5]{L2Ga[EtN−C(O)]2GaL2} ( 6 ), cleavage of the N=C bond with release of 1 equiv. of CO to give [Na(THF)2]2[L2Ga(p-MeC6H4)(N−C(O))2−N(p-MeC6H4)]2 ( 7 ), cleavage of the C=O bond to yield the di-O-bridged digallium compound [Na(THF)3]2[L2Ga-(μ-O)2-GaL2] ( 8 ), and generation of the further addition product [Na2(THF)5][L2Ga(CyNCO2)]2 ( 9 ). Complexes 3 – 9 have been characterized by NMR (1H, 13C), IR spectroscopy, elemental analysis, and X-ray diffraction analysis. Their electronic structures have been examined by DFT calculations. 相似文献
13.
Shubhankar Kumar Bose K. Geetharani V. Ramkumar Shaikh M. Mobin Sundargopal Ghosh Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(48):13483-13490
Reaction of [CpnMCl4?x] (M=V: n=x=2; M=Nb: n=1, x=0) or [Cp*TaCl4] (Cp=η5‐C5H5, Cp*=η5‐C5Me5), with [LiBH4?thf] at ?70 °C followed by thermolysis at 85 °C in the presence of [BH3?thf] yielded the hydrogen‐rich metallaboranes [(CpM)2(B2H6)2] ( 1 : M=V; 2 : M = Nb) and [(Cp*Ta)2(B2H6)2] ( 3 ) in modest to high yields. Complexes 1 and 3 are the first structurally characterized compounds with a metal–metal bond bridged by two hexahydroborate (B2H6) groups forming a symmetrical complex. Addition of [BH3?thf] to 3 results in formation of a metallaborane [(Cp*Ta)2B4H8(μ‐BH4)] ( 4 ) containing a tetrahydroborate ligand, [BH4]?, bound exo to the bicapped tetrahedral cage [(Cp*Ta)2B4H8] by two Ta‐H‐B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two B? H bonds coordinated to the tantalum atoms. All these new metallaboranes have been characterized by mass, 1H, 11B, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1 – 4 . 相似文献
14.
Fu-Chen Liu Jung-Hua Chen Gene-Hsian Lee 《Journal of organometallic chemistry》2006,691(17):3574-3580
Compounds M(η3-C3H5)(CO)2(NCCH3)2(NCBH3) and [N(CH3)4]2[M(η3-C3H5)(CO)2(NCBH3)3] (M = Mo, W) were prepared and structurally characterized. In the solid state, the allyl group orients its open face to the two carbonyl groups producing an endo form in the above compounds. In solution, an exo form coexists with an endo form in compound Mo(η3-C3H5)(CO)2(NCCH3)2(NCBH3). The cyanotrihydroborate ligand bonds to the metal through a nitrogen atom. Both of the IR and the 11B NMR spectroscopic data suggest the negative charge of the cyanotrihydroborate ligand on the complex is almost localized on the BH3 and this negative charge only has small effect on the metal-nitrogen interaction. 相似文献
15.
《Comptes Rendus Chimie》2008,11(8):922-925
The hydrogenase model [Fe2(S2C3H6)(CN)2(CO)4]2− was employed as a molecular tecton for the construction of supramolecular aggregates. IR spectroscopy indicated that cyanide bridged aggregates are formed when [Fe2(S2C3H6)(CN)2(CO)4]2− was treated with Lewis acids such as Zn(tetraphenylporphyrinate), [Cu(NCMe)(2,2′-bipyridine)]PF6 and [Cu(NCMe)4]PF6. Condensation of [Fe2(S2C3H6)(CN)2(CO)4]2− with the tritopic Lewis acid [Cp1Rh]2+ afforded the novel expanded tetrahedron cage, {[Fe2(S2C3H6)(CN)2(CO)4]6[Cp1Rh]4}4−. The tetrahedron cage was characterized crystallographically as the PPN salt. 相似文献
16.
Dr. Jana Schiller Dr. Andrea Schreiner Dr. Michael Seidl Dr. Gábor Balázs Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14570-14574
The reaction of [Cp2Mo2(CO)4(μ,η2:2-E2)] ( A : E=P, B : E=As, Cp=C5H5) with the WCA-containing CuI salts ([Cu(CH3CN)4][Al{OC(CF3)3}4] (CuTEF, C ), [Cu(CH3CN)4][BF4] ( D ) and [Cu(CH3CN)3.5][FAl{OC6F10(C6F5)}3] (CuFAl, E )) affords seven unprecedented coordination compounds. Depending on the E2 ligand complex, the counter anion of the copper salt and the stoichiometry, four dinuclear copper dimers and three trinuclear copper compounds are accessible. The latter complexes reveal first linear Cu3 arrays linked by E2 units (E=P, As) coordinated in an η2:1:1 coordination mode. All compounds were characterized by X-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To define the nature of the Cu⋅⋅⋅Cu⋅⋅⋅Cu interactions, DFT calculations were performed. 相似文献
17.
Toralf Peymann Axel Herzog Carolyn B. Knobler M. Frederick Hawthorne 《Angewandte Chemie (International ed. in English)》1999,38(8):1061-1064
No explosion , but per-B-hydroxylation occurs if the icosahedral boron hydrides [closo-B12H12]2− (see picture), [closo-CB11H12]−, or closo-1,12-(CH2OH)2-1,12-C2B10H10 are refluxed in 30 % hydrogen peroxide. Thus, the three isoelectronic species [closo-B12(OH)12]2−, [closo-1-H-1-CB11(OH)11]−, and closo-1,12-H2-1,12-C2B10(OH)10 were obtained. ○=BH, ○=BOH. 相似文献
18.
Rishabh Gupta Supriya Sahoo Swati Deswal Premkumar Kothavade Prashant Dixit Dr. Jan K. Zaręba Dr. Kadhiravan Shanmuganathan Prof. Dr. Ramamoorthy Boomishankar 《化学:亚洲杂志》2021,16(24):4122-4129
Organic ferroelectrics due to their low cost, easy preparation, light weight, high flexibility and phase stability are gaining tremendous attention in the field of portable electronics. In this work, we report the synthesis, structure and ferroelectric behavior of a two-component ammonium salt 2 , containing a bulky [Bn(4-BrBn)NMe2]+ (Bn=benzyl and 4-BrBn=4-bromobenzyl) cation and tetrahedral (BF4)− anion. The structural analysis revealed the presence of rich non-classical C−H⋅⋅⋅F and C−H⋅⋅⋅Br interactions in this molecule that were quantified by Hirshfeld surface analysis. The polarization (P) vs. electric field (E) hysteresis loop measurements on 2 gave a remnant polarization (Pr) of 14.4 μC cm−2 at room temperature. Flexible polymer composites with various (5, 10, 15 and 20) weight percentages (wt%) of 2 in thermoplastic polyurethane (TPU) were prepared and tested for mechanical energy harvesting applications. A notable peak-to-peak output voltage of 20 V, maximum current density of 1.1 μA cm−2 and power density of 21.1 μW cm−2 were recorded for the 15 wt% 2 -TPU composite device. Furthermore, the voltage output generated from this device was utilized to rapidly charge a 100 μF capacitor, with stored energies and measured charges of 156 μJ and 121.6 μC, respectively. 相似文献
19.
Dr. Sören Arlt Dr. Kevin Bläsing Dr. Jörg Harloff Karoline Charlotte Laatz Dr. Dirk Michalik Simon Nier Prof. Axel Schulz Philip Stoer Dr. Alrik Stoffers Dr. Alexander Villinger 《ChemistryOpen》2021,10(2):62-71
Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non-innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT-IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ-nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa-substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non-innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained. 相似文献
20.
Dr. Luca Rocchigiani Dr. Wim T. Klooster Prof. Dr. Simon J. Coles Dr. David L. Hughes Dr. Peter Hrobárik Prof. Dr. Manfred Bochmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8267-8280
The potential for coordination and H-transfer from Cp2MH2 (M=Zr, W) to gold(I) and gold(III) complexes was explored in a combined experimental and computational study. [(L)Au]+ cations react with Cp2WH2 giving [(L)Au(κ2-H2WCp2)]+ (L=IPr ( 1 ), cyclic (alkyl)(amino)carbene ( 2 ), PPh3 ( 3 ) and Dalphos-Me ( 4 ) [IPr=1,3-bis(diisopropylphenyl)imidazolylidene; Dalphos-Me=di(1-adamantyl)-2-(dimethylamino)phenyl-phosphine], while [Au(DMAP)2]+ (DMAP=p-dimethylaminopyridine) affords the C2-symmetric [Au(κ-H2WCp2)2]+ ( 5 ). The Dalphos complex 4 can be protonated to give the bicationic adduct 4 H, showing AuI⋅⋅⋅H+−N hydrogen bonding. The gold(III) Lewis acid [(C^N−CH)Au(C6F5)(OEt2)]+ binds Cp2WH2 to give an Au-H-W σ-complex. By contrast, the pincer species [(C^N^C)Au]+ adds Cp2WH2 by a purely dative W→Au bond, without Au⋅⋅⋅H interaction. The biphenylyl-based chelate [(C^C)Au]+ forms [(C^C)Au(μ-H)2WCp2]+, with two 2-electron-3-centre W−H⋅⋅⋅Au interactions and practically no Au−W donor acceptor contribution. In all these complexes, strong but polarized W−H bonds are maintained, without H-transfer to gold. On the other hand, the reactions of Cp2ZrH2 with gold complexes led in all cases to rapid H-transfer and formation of gold hydrides. Relativistic DFT calculations were used to rationalize the striking reactivity and bonding differences in these heterobimetallic hydride complexes along with an analysis of their characteristic NMR parameters and UV/Vis absorption properties. 相似文献