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1.
Philipp Dabringhaus Silja Zedlitz Luisa Giarrana David Scheschkewitz Ingo Krossing 《Angewandte Chemie (International ed. in English)》2023,62(8):e202215170
Schnöckel's [(AlCp*)4] and Jutzi's [SiCp*][B(C6F5)4] (Cp*=C5Me5) are landmarks in modern main-group chemistry with diverse applications in synthesis and catalysis. Despite the isoelectronic relationship between the AlCp* and the [SiCp*]+ fragments, their mutual reactivity is hitherto unknown. Here, we report on their reaction giving the complex salts [Cp*Si(AlCp*)3][WCA] ([WCA]−=[Al(ORF)4]− and [F{Al(ORF)3}2]−; RF=C(CF3)3). The tetrahedral [SiAl3]+ core not only represents a rare example of a low-valent silicon-doped aluminium-cluster, but also—due to its facile accessibility and high stability—provides a convenient preparative entry towards low-valent Si−Al clusters in general. For example, an elusive binuclear [Si2(AlCp*)5]2+ with extremely short Al−Si bonds and a high negative partial charge at the Si atoms was structurally characterised and its bonding situation analysed by DFT. Crystals of the isostructural [Ge2(AlCp*)5]2+ dication were also obtained and represent the first mixed Al−Ge cluster. 相似文献
2.
Dr. Jan Bohnenberger Dr. Daniel Kratzert Sai Manoj N. V. T. Gorantla Dr. Sudip Pan Prof. Dr. Gernot Frenking Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(71):17203-17211
The syntheses of the two novel complexes [Ag{Mo/W(CO)6}2]+[F-{Al(ORF)3}2]− (RF=C(CF3)3) are reported along with their structural and spectroscopic characterization. The X-ray structure shows that three carbonyl ligands from each M(CO)6 fragment bend towards the silver atom within binding Ag−C distance range. DFT calculations of the free cations [Ag{M(CO)6}2]+ (M=Cr, Mo, W) in the electronic singlet state give equilibrium structures with C2 symmetry with two bridging carbonyl groups from each hexacarbonyl ligand. Similar structures with C2 symmetry (M=Nb) and D2 symmetry (M=V, Ta) are calculated for the isoelectronic group 5 anions [Ag{M(CO)6}2]− (M=V, Nb, Ta). The electronic structure of the cations is analyzed with the QTAIM and EDA-NOCV methods, which provide detailed information about the nature of the chemical bonds between Ag+ and the {M(CO)6}2q (q = −2, M = V, Nb, Ta; q = 0, M = Cr, Mo, W) ligands. 相似文献
3.
Developments in the chemistry of weakly coordinating anions enabled isolation of numerous unique metal complexes with unusual ligands. An important example is the family of metal-Fe(CO)5 complexes. In the current paper we present synthesis and thorough characterization of the first truly homoleptic {Cu[Fe(CO)5]2}+ cation obtained as a salt of weakly coordinating [Al(ORF)4]− (RF=C(CF3)3) anion. TGA/DSC/MS study show that its decomposition becomes noticeable only above 110 °C, thus it can be stored as powder in air-free conditions for months. The crystal structure of {Cu[Fe(CO)5]2}+ shows strong asymmetry of the cation and very short Cu-CO bonds in comparison to analogous {M[Fe(CO)5]2}+ where M=Ag or Au. Characterization is complemented with analysis of vibrational spectra and extensive DFT calculations which give insight into the energetics of Cu+-Fe(CO)5 systems. Our results show that {Cu[Fe(CO)5]2}+ is homoleptic only as salt of [Al(ORF)4]−. Furthermore, in the presence of additional, even weakly basic ligands, the Cu+-Fe(CO)5 bond strength decreases what may contribute to the complex's instability in liquid SO2 or in the presence of [SbF6]−. These conclusions point at the key role of selection of proper anion and solvent in stabilization of these types of complexes. 相似文献
4.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(11):2926-2930
Truly cationic metallocenes with the parent cyclopentadienyl ligand are so far unknown for the Group 14 elements. Herein we report on an almost “naked” [SnCp]+ cation with the weakly coordinating [Al{OC(CF3)3}4]− and [{(F3C)3CO}3Al−F−Al{OC(CF3)3}3]− anions. [SnCp][Al{OC(CF3)3}4] was used to prepare the first main‐group quadruple‐decker cation [Sn3Cp4]2+ again as the [Al{OC(CF3)3}4]− salt. Additionally, the toluene adduct [CpSn(C7H8)][Al{OC(CF3)3}4] was obtained. 相似文献
5.
《Angewandte Chemie (International ed. in English)》2017,56(11):2880-2884
Truly cationic metallocenes with the parent cyclopentadienyl ligand are so far unknown for the Group 14 elements. Herein we report on an almost “naked” [SnCp]+ cation with the weakly coordinating [Al{OC(CF3)3}4]− and [{(F3C)3CO}3Al−F−Al{OC(CF3)3}3]− anions. [SnCp][Al{OC(CF3)3}4] was used to prepare the first main‐group quadruple‐decker cation [Sn3Cp4]2+ again as the [Al{OC(CF3)3}4]− salt. Additionally, the toluene adduct [CpSn(C7H8)][Al{OC(CF3)3}4] was obtained. 相似文献
6.
Access to the Bis‐benzene Cobalt(I) Sandwich Cation and its Derivatives: Synthons for a “Naked” Cobalt(I) Source? 下载免费PDF全文
Stefan C. Meier Albina Holz Jan Kulenkampff Alexei Schmidt Dr. Daniel Kratzert Dr. Daniel Himmel Dominik Schmitz Dr. Ernst‐Wilhelm Scheidt Prof. Dr. Wolfgang Scherer Dr. Christine Bülow Martin Timm Dr. Rebecka Lindblad Dr. Scott T. Akin Dr. Vicente Zamudio‐Bayer Prof. Dr. Bernd von Issendorff Prof. Dr. Michael A. Duncan Prof. Dr. J. Tobias Lau Prof. Dr. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2018,57(30):9310-9314
The synthesis and structural characterization of the hitherto unknown parent Co(bz)2+ (bz=benzene) complex and several of its derivatives are described. Their synthesis starts either from a CoCO5+ salt, or directly from Co2(CO)8 and a Ag+ salt. Stability and solubility of these complexes was achieved by using the weakly coordinating anions (WCAs) [Al(ORF)4]? and [F{Al(ORF)3}2]? {RF=C(CF3)3} and the solvent ortho‐difluorobenzene (o‐DFB). The magnetic properties of Co(bz)2+ were measured and compared in the condensed and gas phases. The weakly bound Co(o‐dfb)2+ salts are of particular interest for the preparation of further CoI salts, for example, the structurally characterized low‐coordinate 12 valence electron Co(PtBu3)2+ and Co(NHC)2+ salts. 相似文献
7.
Philippe Weis Dr. Ian M. Riddlestone Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(52):12159-12168
The complexes Ag(L)n[WCA] (L=P4S3, P4Se3, As4S3, and As4S4; [WCA]=[Al(ORF)4]− and [F{Al(ORF)3}2]−; RF=C(CF3)3; WCA=weakly coordinating anion) were tested for their performance as ligand-transfer reagents to transfer the poorly soluble nortricyclane cages P4S3, P4Se3, and As4S3 as well as realgar As4S4 to different transition-metal fragments. As4S4 and As4S3 with the poorest solubility did not yield complexes. However, the more soluble silver-coordinated P4S3 and P4Se3 cages were transferred to the electron-poor Fp+ moiety ([CpFe(CO)2]+). Thus, reaction of the silver salt in the presence of the ligand with Fp−Br yielded [Fp−P4S3][Al(ORF)4] ( 1 a ), [Fp−P4S3][F(Al(ORF)3)2] ( 1 b ), and [Fp−P4Se3][Al(ORF)4] ( 2 ). Reactions with P4S3 also yielded [FpPPh3−P4S3][Al(ORF)4] ( 3 ), a complex with the more electron-rich monophosphine-substituted Fp+ analogue [FpPPh3]+ ([CpFe(PPh3)(CO)]+). All complex salts were characterized by single-crystal XRD, NMR, Raman, and IR spectroscopy. Interestingly, they show characteristic blueshifts of the vibrational modes of the cage, as well as structural contractions of the cages upon coordination to the Fp/FpPPh3 moieties, which oppose the typically observed cage expansions that lead to redshifts in the spectra. Structure, bonding, and thermodynamics were investigated by DFT calculations, which support the observed cage contractions. Its reason is assigned to σ and π donation from the slightly P−P and P−E antibonding P4E3-cage HOMO (e symmetry) to the metal acceptor fragment. 相似文献
8.
Shilin Jiang Dr. Jianhui Lan Dr. Lin Wang Dr. Yalan Liu Yuke Zhong Yichuan Liu Dr. Liyong L.-Y. Yuan Dr. Lirong Zheng Prof. Zhifang Chai Prof. Weiqun Shi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(45):11721-11729
Molten salt electrolysis is a vital technique to produce high-purity lanthanide metals and alloys. However, the coordination environments of lanthanides in molten salts, which heavily affect the related redox potential and electrochemical properties, have not been well elucidated. Here, the competitive coordination of chloride and fluoride anions towards lanthanide cations (La3+ and Nd3+) is explored in molten LiCl-KCl-LiF-LnCl3 salts using electrochemical, spectroscopic, and computational approaches. Electrochemical analyses show that significant negative shifts in the reduction potential of Ln3+ occur when F− concentration increases, indicating that the F− anions interact with Ln3+ via substituting the coordinated Cl− anions, and confirm [LnClxFy]3−x−y (ymax=3) complexes are prevailing in molten salts. Spectroscopic and computational results on solution structures further reveal the competition between Cl− and F− anions, which leads to the formation of four distinct Ln(III) species: [LnCl6]3−, [LnCl5F]3−, [LnCl4F2]3− and [LnCl4F3]4−. Among them, the seven-coordinated [LnCl4F3]4− complex possesses a low-symmetry structure evidenced by the pattern change of Raman spectra. After comparing the polarizing power (Z/r) among different metal cations, it was concluded that Ln−F interaction is weaker than that between transition metal and F− ions. 相似文献
9.
10.
Hanieh Roueindeji Antsa Ratsifitahina Dr. Thierry Roisnel Dr. Vincent Dorcet Dr. Samia Kahlal Prof. Dr. Jean-Yves Saillard Prof. Dr. Jean-François Carpentier Dr. Yann Sarazin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8854-8864
A set of calcium and barium complexes containing the fluoroarylamide N(C6F5)2− is presented. These compounds illustrate the key role of stabilising M⋅⋅⋅F−C secondary interactions in the construction of low-coordinate alkaline earth complexes. The nature of Ca⋅⋅⋅F−C bonding in calcium complexes is examined in the light of structural data, bond valence sum (BVS) analysis and DFT computations. The molecular structures of [Ca{N(C6F5)2}2(Et2O)2] ( 4 ′), [Ca{μ-N(SiMe3)2}{N(C6F5)2}]2 ( 52 ), [Ba{μ-N(C6F5)2}{N(C6F5)2}⋅toluene]2 ( 62 ), [{BDIDiPP}CaN(C6F5)2]2 ( 72 ), [{N^NDiPP}CaN(C6F5)2]2 ( 82 ), and [Ca{μ-OB(CH(SiMe3)2)2}{N(C6F5)2}]2 ( 92 ), where {BDIDiPP}− and {N^NDiPP}− are the bidentate ligands CH[C(CH3)NDipp]2− and DippNC6H4CNDipp− (Dipp=2,6-iPr2-C6H3), are detailed. Complex 62 displays strong Ba⋅⋅⋅F−C contacts at around 2.85 Å. The calcium complexes feature also very short intramolecular Ca−F interatomic distances at around 2.50 Å. In addition, the three-coordinate complexes 72 and 82 form dinuclear structures due to intermolecular Ca⋅⋅⋅F−C contacts. BVS analysis shows that Ca⋅⋅⋅F−C interactions contribute to 15–20 % of the bonding pattern around calcium. Computations demonstrate that Ca⋅⋅⋅F−C bonding is mostly electrostatic, but also contains a non-negligible covalent contribution. They also suggest that Ca⋅⋅⋅F−C are the strongest amongst the range of weak Ca⋅⋅⋅X (X=F, H, Cπ) secondary interactions, due to the high positive charge of Ca2+ which favours electrostatic interactions. 相似文献
11.
Mark R. Bortolus Dr. Hélène P. A. Mercier Prof. Gary J. Schrobilgen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8935-8950
The reactions of the fluoride-ion donor, XeF6, with the fluoride-ion acceptors, M′OF4 (M′=Cr, Mo, W), yield [XeF5]+ and [Xe2F11]+ salts of [M′OF5]− and [M2O2F9]− (M=Mo, W). Xenon hexafluoride and MOF4 react in anhydrous hydrogen fluoride (aHF) to give equilibrium mixtures of [Xe2F11]+, [XeF5]+, [(HF)nF]−, [MOF5]−, and [M2O2F9]− from which the title salts were crystallized. The [XeF5][CrOF5] and [Xe2F11][CrOF5] salts could not be formed from mixtures of CrOF4 and XeF6 in aHF at low temperature (LT) owing to the low fluoride-ion affinity of CrOF4, but yielded [XeF5][HF2]⋅CrOF4 instead. In contrast, MoOF4 and WOF4 are sufficiently Lewis acidic to abstract F− ion from [(HF)nF]− in aHF to give the [MOF5]− and [M2O2F9]− salts of [XeF5]+ and [Xe2F11]+. To circumvent [(HF)nF]− formation, [Xe2F11][CrOF5] was synthesized at LT in CF2ClCF2Cl solvent. The salts were characterized by LT Raman spectroscopy and LT single-crystal X-ray diffraction, which provided the first X-ray crystal structure of the [CrOF5]− anion and high-precision geometric parameters for [MOF5]− and [M2O2F9]−. Hydrolysis of [Xe2F11][WOF5] by water contaminant in HF solvent yielded [XeF5][WOF5]⋅XeOF4. Quantum-chemical calculations were carried out for M′OF4, [M′OF5]−, [M′2O2F9]−, {[Xe2F11][CrOF5]}2, [Xe2F11][MOF5], and {[XeF5][M2O2F9]}2 to obtain their gas-phase geometries and vibrational frequencies to aid in their vibrational mode assignments and to assess chemical bonding. 相似文献
12.
Jan Bohnenberger Ingo Krossing 《Angewandte Chemie (International ed. in English)》2020,59(14):5581-5585
The oxidation of Fe(CO)5 with the [NO]+ salt of the weakly coordinating perfluoroalkoxyaluminate anion [F‐{Al(ORF)3}2]? (RF=C(CF3)3) leads to stable salts of the 18 valence electron (VE) species [Fe(CO)4(NO)]+ and [Fe(CO)(NO)3]+ with the Enemark–Feltham numbers of {FeNO}8 and {FeNO}10. This finally concludes the triad of heteroleptic iron carbonyl/nitrosyl complexes, since the first discovery of the anionic ([Fe(CO)3(NO)]?) and neutral ([Fe(CO)2(NO)2]) species over 80 years ago. Both complexes were fully characterized (IR, Raman, NMR, UV/Vis, scXRD, pXRD) and are stable at room temperature under inert conditions over months and may serve as useful starting materials for further investigations. 相似文献
13.
Going Homoleptic: Synthesis and Full Characterization of Stable Manganese Tetranitrosyl Cation Salts
Jan Bohnenberger Brandon Derstine Michael Daub Ingo Krossing 《Angewandte Chemie (International ed. in English)》2019,58(28):9586-9589
Although similar to carbon monoxide, the chemistry of homoleptic nitrogen monoxide complexes is fundamentally unexplored compared to their carbonyl analogues. Herein we report the synthesis of the first truly homoleptic transition‐metal nitrosyl cation as the salt of the weakly coordinating anions (WCAs) [Al(ORF)4]? and [F{Al(ORF)3}2]? (RF=C(CF3)3). These salts are easily accessible in good yields, phase pure, and were fully characterized by IR/Raman, NMR and UV/Vis spectroscopy as well as single‐crystal and powder X‐ray diffraction. They may serve as unprecedented simple model systems for theoretical and experimental studies of nitrosyl complexes. 相似文献
14.
Gui-Xiang Fu Zhang-Lin Zhou Lu Yu Yao-Zeng Huang 《Journal of mass spectrometry : JMS》1992,27(6):695-698
The fast atom bombardment (FAB) mass spectra of telluronium salts were studied. The spectra exhibit the intact cation (C+) and cluster ions ([M + C]+). The principal fragment ions in the FAB mass spectra of telluronium salts are [RTe]+, [R2Te]+˙, [R2Te − H]+, [RTeR′]+˙, and [RTeR′ + H]+. When the anion was [BPh4]−, interesting cluster ions such as [M + C − BPh3]+ appeared. 相似文献
15.
Dr. Fabian Ehret Dr. Vasileios Filippou Svenja Blickle Dr. Martina Bubrin Dr. Stanislav Záliš Prof. Dr. Wolfgang Kaim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3374-3381
Reaction of [Pt(DMSO)2Cl2] or [Pd(MeCN)2Cl2] with the electron-rich LH=N,N’-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2] ( 1 ) but dinuclear [Pd2L4] ( 2 ), a paddle-wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV-vis-NIR spectroscopy, magnetic resonance) and TD-DFT calculations as metal(II) species with noninnocent ligands L−. The reversibly accessible cations [PtL2]+ and [Pd2L4]+ were also studied, the latter as [Pd2L4][B{3,5-(CF3)2C6H3}4] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [PtII(L−)2] or [Pt.(L )2], [PtII(L0.5−)2]+ or [PtIII(L−)2]+, [(PdII)2(μ-L−)4] or [(Pd1.5)2(μ-L0.75−)4], and [(Pd2.5)2(μ-L−)4]+ or [(PdII)2(μ-L0.75−)4]+. In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL2] with an N-Pt-N bite angle of 62.8(2)° in contrast to [Pd2L4], and the dimetal (Pd24+→Pd25+) instead of ligand (L−→L ) oxidation of the dinuclear palladium compound. 相似文献
16.
The pnictocenium salts [Cp*PCl]+[μCl]? ( 1 a ), [Cp*PCl]+[ClAl(ORF)3]? ( 1 b ), [Cp*AsCl]+[ClAl(ORF)3]? ( 2 ), and [(Cp*)2P]+[μCl]? ( 3 ), in which Cp*=Me5C5, μCl=(FRO)3Al? Cl? Al(ORF)3, and ORF=OC(CF3)3, were prepared by halide abstraction from the respective halopnictines with the Lewis superacid PhF→Al(ORF)3. 1 The X‐ray crystal structures of 1 a , 2 , and 3 established that in the half as well as in the sandwich cations the Cp* rings are attached in an η2‐fashion. By using one or two equivalents of the Lewis acid, the two new weakly coordinating anions [μCl]? and [ClAl(ORF)3]? resulted. They also stabilize the highly reactive cations in PhF or 1,2‐F2C6H4 solution at room temperature. The chloride ion affinities (CIAs) of a range of classical strong Lewis acids were also investigated. The calculations are based on a set of isodesmic BP86/SV(P) reactions and a non‐isodesmic reference reaction assessed at the G3MP2 level. 相似文献
17.
Crystal growth from anhydrous hydrogen fluoride solutions of M2+ (M=Cu, Ag) and [AuF6]− gave M(AuF6)2 salts (M=Cu, Ag). Similar attempts to prepare single crystals of the corresponding nickel, zinc and magnesium salts failed. The crystal structure of Cu(AuF6)2 consists of layers of Cu2+ cations connected by [AuF6]− anions, thus forming slabs. Only van der Waals interactions exist between adjacent slabs. The crystal structure of Ag(AuF6)2 consists of a three-dimensional framework in which Ag+ cations are linked by [AuF6]− anions. Both structures are members of the MII(XVF6)2 family, in which seven different structure types have been observed to date. In the crystal structure of O2(CuF)3(AuF6)4 ⋅ HF, the bridging AuF6 units connect [−Cu−F−Cu−F−]∞ chains to form stacks between which O2+ cations and HF molecules are located. 相似文献
18.
Jürgen Pahl Tom E. Stennett Michel Volland Dirk M. Guldi Sjoerd Harder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):2025-2034
[(BDI)Mg+][B(C6F5)4−] ( 1 ; BDI=CH[C(CH3)NDipp]2; Dipp=2,6-diisopropylphenyl) was prepared by reaction of (BDI)MgnPr with [Ph3C+][B(C6F5)4−]. Addition of 3-hexyne gave [(BDI)Mg+ ⋅ (EtC≡CEt)][B(C6F5)4−]. Single-crystal X-ray analysis, NMR investigations, Raman spectra, and DFT calculations indicate a significant Mg-alkyne interaction. Addition of the terminal alkynes PhC≡CH or Me3SiC≡CH led to alkyne deprotonation by the BDI ligand to give [(BDI-H)Mg+(C≡CPh)]2 ⋅ 2 [B(C6F5)4−] ( 2 , 70 %) and [(BDI-H)Mg+(C≡CSiMe3)]2 ⋅ 2 [B(C6F5)4−] ( 3 , 63 %). Addition of internal alkynes PhC≡CPh or PhC≡CMe led to [4+2] cycloadditions with the BDI ligand to give {Mg+C(Ph)=C(Ph)C[C(Me)=NDipp]2}2 ⋅ 2 [B(C6F5)4−] ( 4 , 53 %) and {Mg+C(Ph)=C(Me)C[C(Me)=NDipp]2}2 ⋅ 2 [B(C6F5)4−] ( 5 , 73 %), in which the Mg center is N,N,C-chelated. The (BDI)Mg+ cation can be viewed as an intramolecular frustrated Lewis pair (FLP) with a Lewis acidic site (Mg) and a Lewis (or Brønsted) basic site (BDI). Reaction of [(BDI)Mg+][B(C6F5)4−] ( 1 ) with a range of phosphines varying in bulk and donor strength generated [(BDI)Mg+ ⋅ PPh3][B(C6F5)4−] ( 6 ), [(BDI)Mg+ ⋅ PCy3][B(C6F5)4−] ( 7 ), and [(BDI)Mg+ ⋅ PtBu3][B(C6F5)4−] ( 8 ). The bulkier phosphine PMes3 (Mes=mesityl) did not show any interaction. Combinations of [(BDI)Mg+][B(C6F5)4−] and phosphines did not result in addition to the triple bond in 3-hexyne, but during the screening process it was discovered that the cationic magnesium complex catalyzes the hydrophosphination of PhC≡CH with HPPh2, for which an FLP-type mechanism is tentatively proposed. 相似文献
19.
Dr. Eva‐Maria Rummel Prof. Dr. Piero Mastrorilli Dr. Stefano Todisco Prof. Mario Latronico Dr. Gábor Balázs Dr. Alexander V. Virovets Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2016,55(42):13301-13305
By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}3], [Al{OC(CF3)3}4]), two phosphaalkynes could be coordinated side‐on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] ( 1 ) and [Ag(η2‐P≡CtBu)2][Al{OC(CF3)3}4] ( 2 ). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square‐planar coordination mode of the phosphaalkynes at Ag+ was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH3)2CO)Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] ( 3 ) and [(C7H8)2Ag(η2‐P≡CtBu)][FAl{OC12F15}3] ( 4 ). All of the compounds were comprehensively characterized in solution and in the solid state. 相似文献
20.
Wiebke Unkrig Fu Zhe Razan Tamim Friederike Oesten Dr. Daniel Kratzert Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):758-765
The syntheses of the homoleptic bis(arene) niobium cations [Nb(arene)2]+ (arene = C6H3Me3, C6H5Me) with 16 valence electrons and heteroleptic arene-carbonyl cations [(CO)Nb(arene)2]+ (arene = C6H3Me3, C6H5Me) and [(arene)M(CO)4]+ (arene = C6H3Me3, C6H6) obeying 18 valence electrons are described. Stabilization of these complexes was achieved by using the weakly coordinating anions [Al(ORF)4]− or [F{Al(ORF)3}2]− (RF = C(CF3)3). The limits of two synthesis routes starting from neutral Nb(arene)2 (arene = C6H3Me3, C6H5Me) or [NEt4][M(CO)6] (M = Nb, Ta) were investigated. All compounds were analyzed by single crystal X-ray determination, vibrational and NMR spectroscopy. DFT calculations were executed to support the experimental data. 相似文献