Site‐Directed Dimerization of Bowl‐Shaped Radical Anions to Form a σ‐Bonded Dibenzocorannulene Dimer

Designed site‐directed dimerization of the monoanion radicals of a π‐bowl in the solid state is reported. Dibenzo[a,g]corannulene (C₂₈H₁₄) was selected based on the asymmetry of the charge/spin localization in the C₂₈H₁₄^.? anion. Controlled one‐electron reduction of C₂₈H₁₄ with Cs metal in diglyme resulted in crystallization of a new dimer, [{Cs⁺(diglyme)}₂(C₂₈H₁₄?C₂₈H₁₄)^2?] ( 1 ), as revealed by single crystal X‐ray diffraction study performed in a broad range of temperatures. The C?C bond length between two C₂₈H₁₄^.? bowls (1.560(8) Å) measured at ?143 °C does not significantly change upon heating of the crystal to +67 °C. The single σ‐bond character of the C?C linker is confirmed by calculations. The trans‐disposition of two bowls in 1 is observed with the torsion angles around the central C?C bond of 172.3(5)° and 173.5(5)°. A systematic theoretical evaluation of dimerization pathways of C₂₈H₁₄^.? radicals confirmed that the trans‐isomer found in 1 is energetically favored.     

Self-assembly of tetrareduced corannulene with mixed Li–Rb clusters: dynamic transformations,unique structures and record 7Li NMR shifts

Self-assembly processes of the highly reduced bowl-shaped corannulene generated by the chemical reduction with a binary combination of alkali metals, namely Li–Rb, have been investigated by variable-temperature ¹H and ⁷Li NMR spectroscopy. The formation of several unique mixed metal sandwich products based on tetrareduced corannulene, C₂₀H₁₀ ^4– (1 ^4–), has been revealed followed by investigation of their dynamic transformations in solutions. Analysis of NMR data allowed to propose the mechanism of stepwise alkali metal substitution as well as to identify experimental conditions for the isolation of intermediate and final supramolecular products. As a result, two new triple-decker aggregates with a mixed Li–Rb core, [{Rb(THF)₂}₂]//[Li₃Rb₂(C₂₀H₁₀)₂{Li⁺(THF)}] (2) and [{Rb(diglyme)}₂]//[Li₃Rb₃(C₂₀H₁₀)₂(diglyme)₂]·0.5THF (3·0.5THF), have been crystallized and structurally characterized. The Li₃Rb₂-product has an open coordination site at the sandwich periphery and thus is considered transient on the way to the Li₃Rb₃-sandwich having the maximized intercalated alkali metal content. Next, the formation of the LiRb₅ self-assembly with 1 ^4– has been identified by ⁷Li NMR as the final step in a series of dynamic transformations in this system. This product was also isolated and crystallographically characterized to confirm the LiRb₅ core. Notably, all sandwiches have their central cavities, located in between the hub-sites of two C₂₀H₁₀ ^4– decks, occupied by an internal Li⁺ ion which exhibits the record high negative shift (ranging from –21 to –25 ppm) in ⁷Li NMR spectra. The isolation of three novel aggregates having different Li–Rb core compositions allowed us to look into the origin of the unusual ⁷Li NMR shifts at the molecular level. The discussion of formation mechanisms, dynamic transformations as well as unique electronic structures of these remarkable mixed alkali metal organometallic self-assemblies is provided and supported by DFT calculations.     

Multiple C−H Bond Activations in Corannulene by a Dirhenium Complex

The reaction of Re₂(CO)₈(μ-C₆H₅)(μ-H), 1 with corannulene (C₂₀H₁₀) yielded the product Re₂(CO)₈(μ-H)(μ-η²-1,2-C₂₀H₉), 2 (65 % yield) containing a Re₂ metalated corannulene ligand formed by loss of benzene from 1 and the activation of one of the CH bonds of the nonplanar corannulene molecule by an oxidative-addition to 1 . The corannulenyl ligand has adopted a bridging η²-σ+π coordination to the Re₂(CO)₈ grouping. Compound 2 reacts with a second equivalent of 1 to yield three isomeric doubly metalated corannulene products: Re₂(CO)₈(μ-H)(μ-η²-1,2-μ-η²-10,11-C₂₀H₈)Re₂(CO)₈(μ-H), 3 (35 % yield), Re₂(CO)₈(μ-H)(μ-η²-2,1-μ-η²-10,11-C₂₀H₈)Re₂(CO)₈(μ-H), 4 (12 % yield), and Re₂(CO)₈(μ-H)(μ-η²-1,2-μ-η²-11,10-C₂₀H₈)Re₂(CO)₈(μ-H), 5 (12 % yield), by a second CH activation on a second rim double bond on the corannulene molecule. The isomers differ by the relative orientations of the coordinated Re₂(CO)₈(μ-H) groupings. All new products were characterized structurally by single crystal X-ray diffraction analysis.     

Clamshell Opening in the Mixed‐Metal Supramolecular Aggregates Formed by Fourfold Reduced Corannulene for Maximizing Intercalated Metal Content

The first members of a new class of supramolecular organometallic compounds with mixed‐alkali‐metal cluster cores, LiK₅ and Li₃K₃, sandwiched between two four‐fold reduced corannulene decks are prepared and fully characterized. The triple‐decker supramolecular anions, [(C₂₀H₁₀^4?)(LiK₅)⁶⁺(C₂₀H₁₀^4?)]^2? and [(C₂₀H₁₀^4?)(Li₃K₃)⁶⁺(C₂₀H₁₀^4?)]^2?, illustrate a record ability of bowl‐shaped and highly charged corannulene to provide all its sites, five benzene rings fused to a central five‐membered ring, for binding of six alkali‐metal ions. The previously unseen engagement of the hub‐site of C₂₀H₁₀^4? in lithium binding is accompanied by unprecedented shifts up to ?24 ppm in ⁷Li NMR spectra. The discussion of product formation mechanism, augmented by calculations, is provided.     

Molecular Structure and Magnetic and Optical Properties of Endometallonitridofullerene Sc3N@Ih-C80 in Neutral,Radical Anion,and Dimeric Anionic Forms

A series of compounds with Sc₃N@I_h-C₈₀ in the neutral, monomeric, and dimeric anion states have been prepared in the crystalline form and their molecular structures and optical and magnetic properties have been studied. The neutral Sc₃N@I_h-C₈₀ ⋅ 3 C₆H₄Cl₂ ( 1 ) and (Sc₃N@I_h-C₈₀)₃(TPC)₂ ⋅ 5 C₆H₄Cl₂ ( 2 , TPC=triptycene) compounds both crystallized in a high-symmetry trigonal structure. The reduction of Sc₃N@I_h-C₈₀ to the radical anion resulted in dimerization to form diamagnetic singly bonded (Sc₃N@I_h-C₈₀⁻)₂ dimers. In contrast to {[2.2.2]cryptand(Na⁺)}₂(Sc₃N@I_h-C₈₀⁻)₂ ⋅ 2.5 C₆H₄Cl₂ ( 3 ) with strongly disordered components, we synthesized new dimeric phases {[2.2.2]cryptand- (K⁺)}₂(Sc₃N@I_h-C₈₀⁻)₂ ⋅ 2 C₆H₄Cl₂ ( 4 ) and {[2.2.2]cryptand- (Cs⁺)}₂(Sc₃N@I_h-C₈₀⁻)₂ ⋅ 2 C₆H₄Cl₂ ( 5 ) in which only one major dimer orientation was found. The thermal stability of the (Sc₃N@I_h-C₈₀⁻)₂ dimers was studied by EPR analysis of 3 to show their dissociation in the 400–460 K range producing monomeric Sc₃N@I_h-C₈₀^.− radical anions. This species shows an EPR signal with a hyperfine splitting of 5.8 mT. The energy of the intercage C−C bond was estimated to be 234±7 kJ mol⁻¹, the highest value among negatively charged fullerene dimers. The EPR spectra of crystalline (Bu₃MeP⁺)₃(Sc₃N@I_h-C₈₀^.−)₃ ⋅ C₆H₄Cl₂ ( 6 ) are presented for the first time. The salt shows an asymmetric EPR signal, which could be fitted by three lines. Two lines were attributed to Sc₃N@I_h-C₈₀^.−. Hyperfine splitting is manifested above 180 K due to the hyperfine interaction of the electron spin with the three scandium atoms (a total of 22 lines with an average splitting of 5.32 mT are observed at 220 K). Furthermore, each of the 22 lines is additionally split into six lines with an average separation of 0.82 mT. The large splitting indicates intrinsic charge and spin density transfer from the fullerene cage to the Sc₃N cluster. Both the monomeric and dimeric Sc₃N@I_h-C₈₀⁻ anions show an intrinsic shift of the IR bands attributed to the Sc₃N cluster and new bands corresponding to these species appear in the NIR range of their UV/Vis/NIR spectra, which allows these anions to be distinguished from neutral species.     

Synthesis and x-ray crystallographic structural determination of the acetylene complex (η5−C5H5)2W2(CO)4(C2H2)

Reaction of photogenerated (η⁵?C₅H₅)₂W₂(CO)₄ with acetylene at 25°C yields a complex of the formula (η⁵-C₅H₅)₂W₂(CO)₄(C₂H₂). The crystal structure of the complex shows it to have a tetrahedrane-like W₂C₂ core. The C—C bond distance of the C₂H₂ unit is 1.33 Å which is close to that of ethylene, considerably longer than the 1.20 Å for acetylenes. The W—W distance is 2.987 Å which is ～0.25 Å shorter than the W—W distance in (η⁵-C₅H₅)₂W₂(CO)₆ but longer than that expected for (η⁵-C₅H₅)₂W₂(CO)₄. By analogy to the parent (η⁵-C₅H₅)₂M₂(CO)₆ species, the near-UV absorption in (η⁵-C₅H₅)₂M₂(CO)₄(C₂H₂) is assigned to a σ_b → σ^* transition. Owing to the shorter M—M bond in the C₂H₂ adducts, the σ_b → σ^* absorption is at higher energy than in the (η⁵-C₅H₅)₂M₂(CO)₆ complexes.     

Monoreduced 1,2‐dihydrocorannulene versus the parent corannulene

The monoanion of dihydrogenated corannulene isolated in the form of its potassium salt, namely tris(diglyme‐κ³O,O′,O′′)potassium hexacyclo[11.5.2.0^4,17.0^7,16.0^10,15.0^14,18]icosa‐1,3,5,7(16),8,10(15),11,13,17‐nonaenide, [K(C₆H₁₄O₃)₃](C₂₀H₁₂), has been structurally characterized for the first time. The X‐ray study confirms the previous NMR spectroscopic prediction that the two H atoms are attached to the same six‐membered ring to form 1,2‐dihydrocorannulene, thus destroying the aromaticity of only one arene ring of the corannulene core. The direct comparison of (C₂₀H₁₂)⁻ with the parent corannulene anion, (C₂₀H₁₀)⁻, is provided to illustrate the geometry perturbations caused by rim hydrogenation.     

Indeno[2,1-a]fluorene-11,12-dione Radical Anions: Synthesis,Characterization, and Properties

The one-electron reduction of indeno[2,1-a]fluorene-11,12-dione ( IF ) with various alkali metals prepare the radical anion salts. The data about different structures, properties, and characterization was obtained by single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) spectroscopy, superconducting quantum interference device (SQUID) measurements, and physical property measurement system (PPMS). Compound IF ^.−K⁺(18-c-6) is regarded as a one-dimensional magnetic chain through C−H⋅⋅⋅C interaction. Theoretical calculations and magnetic results showed that [ IF ^.−K⁺(15-c-5)]₂ is a dimer with an open-shell ground state. Compounds IF ^.−Na⁺(15-c-5) and IF ^.−K⁺(cryptand) are monoradical anion salts: IF ₂^.−Li⁺ possesses unique π-stack structure with an interplanar separation less than 3.46 Å, making it a semiconductor (δ_RT=1.9×10⁻⁴ S ⋅ cm⁻¹). This work gives insights into multifunctional radical anions, and describes the design and development of different functional radicals.     

Elektronenreiche Phenylkomplexe der Übergangsmetalle. II. Li4Co2(C6H5)4 · 4THF,Li4Co2(C6H5)4 · 3 Dioxan und Li3Co(C6H5)2(LiC6H5) · 5THF,die ersten Komplexe mit einer Bis(phenyl)cobalt(0)- und -cobalt(-I)-Einheit

Electron-rich Phenyl Complexes of Transition Metals. II. Li₄Co₂(C₆H₅)₄ · 4THF, Li₄Co₂(C₆H₅)₄ · 3 Dioxan and Li₃Co(C₆H₅)₂(LiC₆H₅) · 5THF, the First Complexes with a Bis(phenyl)-cobalt(0)- and -cobalt(-I) Unity . Li₂Co^II(C₆H₅)₄ · 4THF reacts spontaneously in benzene by splitting off of two phenyl radicals to a dimeric bis(phenyl) cobalt(0) complex which has been isolated as a THF and a dioxan adduct Li₄Co₂(C₆H₅)₄ · 4THF and Li₄Co₂(C₆H₅)₄ · 3 Dioxan, respectively. Reduction with lithiumphenyl in ether gives a phenyl cobalt(-I) complex Li₄Co(C₆H₅)₃ · 5THF containing besides σ-bonded phenyl anions lithium phenyl coordinated to cobalt in a π-complex like manner, proved by means of ¹³C? NMR-spectroscopy. The stabilization of the low oxidation states is explained by coordination of the lithium ions to cobalt by multiple center bonds, and for each compound a plausible structure is derived.     

Ligand-centred coupling of the alkynyl radical cations [Mo(CCR)(Ph2PCH2CH2PPh2)(η-C7H7)]+ (R = Ph or Bun: crystal structure of the dimeric product [Mo2(Ph2PCH2CH2PPh2)2(η-C7H7)2(μ-C4R2)][PF6]2 (R = Ph)

The radical cations [Mo(CCR)(dppe)(η-C₇H₇)]⁺ (R = Ph or Buⁿ); dppe = Ph₂PCH₂CH₂PPh₂) undergo coupling at C_β of the alkynyl ligand to afford the divinylidene-bridged, dimeric products [Mo₂(dppe)₂(η-C₇H₇)₂(μ-C₄R₂)]²⁺, characterised crystallographically for R = Ph.     

Palladium π-adduct of corannulene

The ternary palladium π-adduct of corannulene and benzene, [Pd₆Cl₁₂·(C₂₀H₁₀)₂·(C₆H₆)₂]·C₆H₆ (1), has been prepared by reacting the cubic Pd₆Cl₁₂-cluster with C₂₀H₁₀ in benzene. It was structurally characterized to reveal η¹-binding of Pd₆Cl₁₂ to a hub C-atom of the convex surface of corannulene (Pd?C, 3.085(3) Å) and its η⁶-complexation to benzene (Pd?C_centroid, 3.431(3) Å). The behavior and persistence of 1 in some aromatic solvents has been revealed by UV-vis and ¹H NMR spectroscopy studies.     

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren‐9‐olato− Anions and Indium(III) Phthalocyanine Bromide Radical Anions

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu₄N⁺)₂[M^III(HFl−O⁻)(Pc^.3−)]^.−(Br⁻) ⋅ 1.5 C₆H₄Cl₂ [M=Al ( 1 ), Ga ( 2 ); HFl−O⁻=fluoren‐9‐olato⁻ anion; Pc=phthalocyanine] and (Bu₄N⁺) [In^IIIBr(Pc^.3−)]^.− ⋅ 0.875 C₆H₄Cl₂ ⋅ 0.125 C₆H₁₄ ( 3 ). The salts were found to contain Pc^.3− radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc^.3− in the near‐IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl−O⁻ anions in 1 and 2 with short Al−O and Ga−O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C−O bonds [1.402(3) and 1.391(11) Å in 1 and 2 , respectively] in the HFl−O⁻ anions are longer than the same bond in the fluorenone ketyl (1.27–1.31 Å). Salts 1 – 3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ_B at 300 K, respectively, owing to the presence of unpaired S= 1/2 spins on Pc^.3−. These spins are coupled antiferromagnetically with Weiss temperatures of −22, −14, and −30 K for 1 – 3 , respectively. Coupling can occur in the corrugated two‐dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J /k _B=−0.9 and −1.1 K, respectively, and in the π‐stacking {[In^IIIBr(Pc^.3−)]^.−}₂ dimers of 3 with an exchange interaction of J /k _B=−10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc^.3−. It was found that increasing the size of the central metal atom strongly broadened these EPR signals.     

Photoinduced Electron Transfer in Tetrathiafulvalene−Porphyrin−Fullerene Molecular Triads

The two molecular triads 1a and 1b consisting of a porphyrin (P) covalently linked to a fullerene (C₆₀) electron acceptor and tetrathiafulvalene (TTF) electron‐donor moiety were synthesized, and their photochemical properties were determined by transient absorption and emission techniques. Excitation of the free‐base‐porphyrin moiety of the TTF−P_{2 H}−C₆₀ triad 1a in tetrahydro‐2‐methylfuran solution yields the porphyrin first excited singlet state TTF−¹P_{2 H}−C₆₀, which undergoes photoinduced electron transfer with a time constant of 25 ps to give TTF−P_{2 H}^.+−C₆₀^.−. This intermediate charge‐separated state has a lifetime of 230 ps, decaying mainly by a charge‐shift reaction to yield a final state, TTF^.+−P_{2 H}−C₆₀^.−. The final state has a lifetime of 660 ns, is formed with an overall yield of 92%, and preserves ca. 1.0 eV of the 1.9 eV inherent in the porphyrin excited state. Similar behavior is observed for the zinc analog 1b . The TTF‐P_Zn^.+−C₆₀^.− state is formed by ultrafast electron transfer from the porphyrinatozinc excited singlet state with a time constant of 1.5 ps. The final TTF^.+−P_Zn−C₆₀^.− state is generated with a yield of 16%, and also has a lifetime of 660 ns. Although charge recombination to yield a triplet has been observed in related donor‐acceptor systems, the TTF^.+−P−C₆₀^.− states recombine to the ground state, because the molecule lacks low‐energy triplet states. This structural feature leads to a longer lifetime for the final charge‐separated state, during which the stored energy could be harvested for solar‐energy conversion or molecular optoelectronic applications.     

Cyclopentadienyl-ruthenium and -osmium chemistry : XXXIX. Syntheses of novel alkynyl-ruthenium complexes. X-Ray structures of two forms of {Ru(PPh3)2(η-C5H5)}2(μ-C4) and of Ru{CCC(O)Me}(PPh3)2(η-C5H5)

Reactions between [Ru(thf)(PPh₃)₂(η-C₅H₅)]⁺ and lithium acetylides have given further examples of substituted ethynylruthenium complexes that are useful precursors of allenylidene and cumulenylidene derivatives. From Li₂C₄, mono- and bi-nuclear ruthenium complexes were obtained: single-crystal X-ray studies have characterised two rotamers of {Ru(PPh₃)₂(η-C₅H₅)}₂(μ-C₄), which differ in the relative cis and trans orientations of the RuL_n groups. Protonation of Ru(CCCCH)(PPh₃)₂(η-C₅H₅) afforded the butatrienylidene cation [Ru(C=C=C=CH₂)(PPh₃)₂(η-C₅H₅)]⁺, which reacted readily with atmospheric moisture to give the acetylethynyl complex Ru{CCC(O)Me}(PPh₃)₂(η-C₅H₅), also fully characterised by an X-ray structural study.     

Nickelocene chemistry : II. New methylidyne trinickel cluster compounds

The new methylidene trinickel cluster complexes, [RCNi₃(η⁵-C₅H₅₃] (R  CMe₃ or SiMe₃) and [Me₃SiCNi₃(η⁵-C₅H₅)2(η⁵-C₅H₄CH₂SiMe₃)] have been isolated in low yield from reactions between nickelocene and the corresponding alkyllithium reagents, RCH₂Li. The compounds [RCNi₃(η⁵-C₅H₅)₃] (R  Ph, CMe₃ or SiMe₃) have also been obtained by treatment of the σ-alkylnickel complexes [(η⁵-C₅H₅)Ni(CH₂R)(PPh₃)] with n-BuLi in the presence of an excess of nickelocene, but under similar conditions [(η⁵-C₅H₅)Ni(CH₂C_1OH₇-2)-(PPh₃)] (where C_1OH₇-2  2-naphthyl) failed to give [2-C_1OH₇CNi₃(η⁵-C₅H₅)₃]. The attempted synthesis of [(η⁵-C₅H₅)Ni(CH₂CCH)(PPh₃)] from [(η⁵-C₅H₅)-NiBr(PPh₃)] and CHCCH₂MgBr gave only [(η⁵-C₅H₅)Ni(CCMe)(PPh₃)] by an unusual rearrangement reaction.     

Säureinduzierte carbin-acylumwandlung

The reaction of dicarbonyl- and carbonyl(trimethylphosphine)(cyclopentadienyl)-carbyne complexes of molybdenum and tungsten η⁵-C₅H₅(CO)_2−n(PMe₃)_nMCR (n = 0, 1; M = Mo, W; R = CH₃, C₆H₅, C₆H₄CH₃, C₃H₅) with protic nucleophiles HX (X = Cl, CF₃COO, CCl₃COO) leads, through a combined protonation/carbon-carbon coupling reaction, to η²-acyl complexes η⁵-C₅H₅(CO)_1−nX₂(PMe₃)_n-M(η²-COCH₂R). The reaction conditions, the results of the spectroscopic measurements and the X-ray structure of η⁵-C₅H₅(CO)(Cl₂)W(η²-COCH₂CH₃) are reported.     

Sandwich complexes of Si, Ge, Sn, and Pb with cyclopentadienyl type derivatives of corannulene and fullerene C60: stability estimates and molecular and electronic structure prediction by the MNDO/PM3 method

The ability of cyclopentadienyl type derivatives of corannulene C₂₀H₁₀ and fullereneI _h -C₆₀ to form η⁵-π-complexes and the problem of their existence is discussed. MNDO/PM3 calculations of half-sandwich complexes η⁵-π-MC₂₀H₁₅, η⁵-π-MC₂₀H ₁₅ ⁺ , η⁵-π-MC₆₀H₅, η⁵-π-MC₆₀H₅ and sandwich complexes 2η⁵-π-M(C₂₀H₁₅)₂, 2η⁵-π-M(C₂₀H₁₅)₂, 2η⁵-π-M(C₆₀H₅)₂ (M=Si, Ge, Sn, Pb) were performed. For all systems studied, local minima were found on corresponding potential energy surfaces and the heats of formation, geometric parameters, and distributions of effective atomic charges were calculated. Sandwich complexes are most likely to exist with M=Si and Ge. The energy and geometric characteristics of η⁵-π-complexes of corannulene were compared with those of η⁵-π-complexes of fullereneI _h -C₆₀. It was concluded that the results of quantum-chemical calculations of sandwich type corannulene derivatives can be used for simulation of the geometry and electronic structure of analogous complexes of fullereneI _h -C₆₀. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1656, September, 1999.     

Organo‐Palladium(II)‐Verbindungen mit PdC4‐Koordination: Phenylethinyl‐ und Methylphenylethinylkomplexe

Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd₂(acac)₂(oxam)]) reacted with Li–C≡C–C₆H₅ in THF with formation of [Pd(C≡C–C₆H₅)₄Li₂(thf)₄] ( 1a ). Reaction of [Pd₂(acac)₂(oxam)] with a mixture of 6 equiv. Li–C≡C–C₆H₅ and 2 equiv. LiCH₃ resulted in the formation of [Pd(CH₃)(C≡C–C₆H₅)₃Li₂(thf)₄] ( 2 ), and the dimeric complex [Pd₂(CH₃)₄(C≡C–C₆H₅)₄Li₄(thf)₆] ( 3 ) was isolated upon reaction of [Pd₂(acac)₂(oxam)] with a mixture of 4 equiv. Li–C≡C–C₆H₅ and 4 equiv. LiCH₃. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, ¹H‐, ¹³C‐, ⁷Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh₃)₄ in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C₆H₅)₂(PPh₃)₂] and [Pd(η²‐O₂)(PPh₃)₂]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction.     

Synthesis and reactivity of [2]disilaniobocenophanes

The paramagnetic ansa-niobocene [(Me₂Si)₂(η⁵-C₅H₄)₂NbCl₂] (1) was obtained from the reaction of Li₂[(Me₂Si)₂(C₅H₄)₂] with [NbCl₄(thf)₂]. Further treatment with Li[AlH₄] yielded [(Me₂Si)₂(η⁵-C₅H₄)₂NbH₃] (3), which is prone to decomposition within a few days at room temperature both in solution and in the solid-state, thus affording primarily an insoluble black material. However, after heating or irradiation of a solution of 3 small quantities of the dimeric niobium hydride species, [(Me₂Si)₂{μ-(η¹:η⁵-C₅H₃)}(η⁵-C₅H₄)NbH]₂ (4), were isolated and characterized by X-ray diffraction.     

Theoretical study of a novel organic electride with large nonlinear optical responses

The design of stable organic electrides with high nonlinear optical (NLO) properties is a challenge in organic and materials chemistry. Here we theoretically design of a novel organic molecular electride model, Li⁺(C₂₀H₁₅Li₅)e⁻, by modifying the lithiation and Li-doping based on dodecahedrane (C₂₀H₂₀). Its electride characteristic is verified by the quantum theory of atoms in molecules and electron localization function analyses. For the first time, the strategy of steric protection is applied to improve the stability of the organic electride Li⁺@(C₂₀H₁₅Li₅)e⁻, in which the closed C₂₀ cage serves not only as the ligand with a negative inner electric field to stabilize the Li cation but also as a barrier to prevent the Li cation from escaping. Meanwhile, the released excess electron is firmly captured in the cavity of Li₅. Moreover, Li⁺(C₂₀H₁₅Li₅)e⁻ displays a remarkably large first hyperpolarizability of 1.4 × 10⁴ au with potential application in organic second-order NLO materials.