Regioselective Derivatization of Silylated [20]Silafulleranes.

Silafulleranes with endohedral Cl- ions are a unique, scarcely explored class of structurally well-defined silicon clusters and host-guest complexes. Herein, we report regioselective derivatization reactions on the siladodecahedrane [nBu4N][Cl@Si20(SiCl3)12Cl8] ([nBu4N][1]), which has its cluster surface decorated with 12 SiCl3 and 8 Cl substituents in perfect Th symmetry. The room-temperature reaction of [nBu4N][1] with excess iBu2AlH in ortho-difluorobenzene (oDFB) furnishes perhydrogenated [nBu4N][Cl@Si20(SiH3)12H8] ([nBu4N][2]) in 50% yield; the non-pyrophoric [2]- is the largest structurally authenticated (by X-ray diffraction) hydridosilane known to date. A simple switch from pure oDFB to an oDFB/Et2O solvent mixture suppresses core hydrogenation and results in the formation of [nBu4N][Cl@Si20(SiH3)12Cl8] ([nBu4N][3]). In addition to the exhaustive Cl/H exchange at all 44 Si-Cl bonds of [1]- and the regioselective 36-fold silyl group hydrogenation, we achieved the simultaneous introduction of Me substituents at all 8 SiCl vertices along with the conversion of all 12 SiCl3 to SiH3 groups by treating [nBu4N][1] with Me2AlH/Me3Al in oDFB ([nBu4N][Cl@Si20(SiH3)12Me8], [nBu4N][4]; 73%). Quantum-chemical free-energy calculations find an SN2-Si-type hydrogenation of the exohedral SiCl3 moieties in [1]- (trigonal-bipyramidal intermediate) slightly preferred over metathesis-like SNi-Si substitutions (four-membered transition state). Cage hydrogenation likely occurs via SNi-Si processes. The experimentally demonstrated influence of an Et2O co-solvent, which drastically increases the respective reaction barriers, is attributed to the increased stability of the resulting iBu2AlH-OEt2 adduct and its higher steric bulk compared to free iBu2AlH.

Synthesis, bridgehead functionalization, and photoisomerization of 9,10-diboratatriptycene dianions.

9,10-Diboratatriptycene salts M2[RB(µ-C6H4)3BR] (R = H, Me; M+ = Li+, K+, [n-Bu4N]+) have been synthesized via [4 + 2] cycloaddition between doubly reduced 9,10-dihydro-9,10-diboraanthracenes M2[DBA] and benzyne, generated in situ from C6H5F and C6H5Li or LiN(i-Pr)2. [HB(µ-C6H4)3BH]2- reacts with CH2Cl2 to form quantitatively the bridgehead-derivatized [ClB(µ-C6H4)3BCl]2-, while twofold H- abstraction with B(C6F5)3 in the presence of SMe2 leads cleanly to the diadduct (Me2S)B(µ-C6H4)3B(SMe2). Photoisomerization of K2[HB(µ-C6H4)3BH] (THF, medium-pressure Hg lamp) provides facile access to diborabenzo[a]fluoranthenes, a little explored form of boron-doped polycyclic aromatic hydrocarbons. According to DFT calculations, the underlying reaction mechanism consists of three main steps: (i) photoinduced di-π-borate rearrangement, (ii) "walk reaction" of a BH unit, and (iii) boryl anion-like C-H activation.

Catalyst-free diboration and silaboration of alkenes and alkynes using bis(9-heterofluorenyl)s.

Diboration and silaboration reactions are prominent tools to introduce valuable functional groups into organic substrates. To date, most diboranes(4) and silylboranes used for this purpose are electronically and/or kinetically stabilized and require activation by a catalyst. We show here that the tetraaryl (µ-hydrido)diborane(4) anion [3]- and the silyl (hydrido)borate ([4]-)/Me3SiBr system react spontaneously with the archetypal olefin ethylene in the absence of a catalyst. The actual active species in both cases are the valence isoelectronic intermediates [FluB-B(H)Flu]- ([1]-) and FluB-Si(H)Flu (2), which consist of two 9-heterofluorenyl halves that get attached to the 1 and 2 positions of ethylene. At room temperature, [1]- is present in a dynamic equilibrium with its isolable isomer [3]-, while 2 has to be released in situ at low temperatures by H- abstraction from [4]-. Quantum-chemical calculations show qualitatively identical reaction mechanisms for [1]- and 2. Since the reactions start with π coordination of the ethylene molecule to a vacant B(pz) orbital, the high Lewis acidity and low steric hindrance of the 9-borafluorenyl fragments are the keys to success. As the reaction proceeds, back-donation from the B-E bond into the ethylene π* orbital becomes increasingly important (E = B, Si). The scope of the reactions has been extended to tBu(H)C[double bond, length as m-dash]CH2 and tBuC[triple bond, length as m-dash]CH on the one hand and FluB-Si(Cl)Flu as well as FluB-Si(Cl)Ph2 on the other.

Crystal structure of [tBuMgCl]2[MgCl2(Et2O)2]2.

The title compound, di-µ3-chlorido-tetra-µ2-chlorido-tetra-kis-(diethyl ether-κO)bis-(1,1-di-methyl-eth-yl)tetra-magnesium, [Mg4(C4H9)2Cl6(C4H10O)4], features an Mg4Cl6 open-cube cluster. The two four-coordinate Mg2+ ions show an almost tetra-hedral coordination, whereas the two six-coordinate Mg2+ ions have their ligands in an octa-hedral environment. The Mg-Cl bond lengths differ depending on the coordination number (2 or 3) of the bridging µ-Cl- ligands. There are few comparable structures deposited in the Cambridge Structural Database.

Group IV heteroadamantanes: synthesis of Si6Sn4 and site-selective derivatization of Si6Ge4.

The mixed heteroadamantanes Si6Ge4 and Si6Sn4 are readily accessible from Me2ECl2/Si2Cl6/cat. Cl- (4 × EMe2, 2 × SiCl2, 4 × Si-SiCl3 vertices; E = Ge, Sn). Different from Si6Ge4, two skeletal isomers are formed in the case of Si6Sn4. Site-selective SiCl3-methylation of Si6Ge4 was achieved, leaving the SiCl2 groups untouched.

Multifaceted behavior of a doubly reduced arylborane in B-H-bond activation and hydroboration catalysis.

Alkali-metal salts of 9,10-dimethyl-9,10-dihydro-9,10-diboraanthrancene (M2[DBA-Me2]; M+ = Li+, Na+, K+) activate the H-B bond of pinacolborane (HBpin) in THF already at room temperature. For M+ = Na+, K+, the addition products M2[4] are formed, which contain one new H-B and one new B-Bpin bond; for M+ = Li+, the H- ion is instantaneously transferred from the DBA-Me2 unit to another equivalent of HBpin to afford Li[5]. Although Li[5] might commonly be considered a [Bpin]- adduct of neutral DBA-Me2, it donates a [Bpin]+ cation to Li[SiPh3], generating the silyl borane Ph3Si-Bpin; Li2[DBA-Me2] with an aromatic central B2C4 ring acts as the leaving group. Furthermore, Li2[DBA-Me2] catalyzes the hydroboration of various unsaturated substrates with HBpin in THF. Quantum-chemical calculations complemented by in situ NMR spectroscopy revealed two different mechanistic scenarios that are governed by the steric demand of the substrate used: in the case of the bulky Ph(H)C[double bond, length as m-dash]NtBu, the reaction requires elevated temperatures of 100 °C, starts with H-Bpin activation which subsequently generates Li[BH4], so that the mechanism eventually turns into "hidden borohydride catalysis". Ph(H)C[double bond, length as m-dash]NPh, Ph2C[double bond, length as m-dash]O, Ph2C[double bond, length as m-dash]CH2, and iPrN[double bond, length as m-dash]C[double bond, length as m-dash]NiPr undergo hydroboration already at room temperature. Here, the active hydroboration catalyst is the [4 + 2] cycloadduct between the respective substrate and Li2[DBA-Me2]: in the key step, attack of HBpin on the bridging unit opens the bicyclo[2.2.2]octadiene scaffold and gives the activated HBpin adduct of the Lewis-basic moiety that was previously coordinated to the DBA-B atom.

Dope it with germanium: selective access to functionalized Si5Ge heterocycles.

The Cl- diadduct [nBu4N]2[A·2Cl] of the mixed cyclohexatetrelane (SiCl2)5(GeMe2), A, is accessible from Me2GeCl2, 6 eq. Si2Cl6, and 2 eq. [nBu4N]Cl in one step (96%). Free, tenfold functionalized A can be released from the primary product by decomplexation with AlCl3 (78%). Insight into the assembly mechanism of [nBu4N]2[A·2Cl] and the reactivity of A is provided.

(BO)2-Doped Tetrathia[7]helicene: A Configurationally Stable Blue Emitter.

Helicenes combine two central themes in chemistry: extended π-conjugation and chirality. Heteroatom doping preserves both characteristics and allows to modulate the electronic structure of a helicene. Herein, we report the (BO)2-doped tetrathia[7]helicene 1, which was prepared from 2-methoxy-3,3'-bithiophene via four steps. 1 is formally derived by substituting two (Mes)B-O moieties in place of (H)C=C(H) fragments in two benzene rings of parent tetrathia[7]helicene. X-ray crystallography revealed a dihedral angle of 50.26(9)° between the two terminal thiophene rings. (P)-/(M)-1 enantiomers were separated by chiral-HPLC and are configurationally stable at room temperature. The experimentally determined enantiomerization barrier of 27.4 ± 0.1 kcal mol-1 is lower than that of tetrathia[7]helicene (39.4 ± 0.1 kcal mol-1). Circular dichroism spectra of (P)- and (M)-1 show a perfect mirror-image relationship. 1 is a blue emitter (λem = 411 nm) with a photoluminescence quantum efficiency of ΦPL = 6% (cf. tetrathia[7]helicene: λem ≈ 405 nm, ΦPL = 5%).

A Hydride-Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)-Dianion Isostere?

The B-nucleophilic 9H-9-borafluorene dianion reacts with 9-chloro-9-silafluorene to afford air- and moisture-stable silylborate salts M[Ar2 (H)B-Si(H)Ar2 ] (M[HBSiH], M=Li, Na). Li[HBSiH] and Me3 SiCl give the B-pyridine adduct Ar2 (py)B-Si(H)Ar2 ((py)BSiH) or the chlorosilane Li[Ar2 (H)B-Si(Cl)Ar2 ] (Li[HBSiCl]) in C6 H6 -pyridine or THF. In both cases, the first step is H- abstraction at the B center. The resulting free borane subsequently binds a py or thf ligand. While the py adduct is stable at room temperature, the thf adduct undergoes a 1,2-H shift via the cyclic B(µ-H)Si intermediate BHSi, which is afterwards attacked at the Si atom by a Cl- ion to give Li[HBSiCl]. DFT calculations were employed to support the proposed reaction mechanism and to characterize the electronic structure of BHSi. Treatment of Li[HBSiCl] with the N-heterocyclic carbene IMe introduces the neutral donor at the Si atom and leads to Ar2 (H)B-Si(IMe)Ar2 (HBSi(IMe)), a donor-acceptor-stabilized silylene.

Mixed-Substituted Single-Source Precursors for Si1-xGex Thin Film Deposition.

A series of new mixed-substituted heteronuclear precursors with preformed Si-Ge bonds has been synthesized via a two-step synthesis protocol. The molecular sources combine convenient handling with sufficient thermal lability to provide access to group IV alloys with low carbon content. Differences in the molecule-material conversion by chemical vapor deposition (CVD) techniques are described and traced back to the molecular design. This study illustrates the possibility of tailoring the physical and chemical properties of single-source precursors for their application in the CVD of Si1-xGex coatings. Moreover, partial crystallization of the Si1-xGex has been achieved by Ga metal-supported CVD growth, which demonstrated the potential of the presented precursor class for the synthesis of crystalline group IV alloys.

Charge-Transfer Transitions Govern the Reactivity and Photophysics of Vicinally Diphosphanyl-Substituted Diborapentacenes.

2,3-Difluoro-5,14-dihydro-5,14-diborapentacene (DBP) was endowed with two vicinal Ph2 P groups by an SN Ar reaction at both CF sites using Ph2 PSiMe3 . Computations reveal the ambipolar product P to undergo P-to-B charge transfer under ambient light irradiation. Consequently, P is prone to photooxidation by air, yielding the Ph2 P(O) species PO. With S8 or [Me3 O][BF4 ], P furnishes the Ph2 P(S) or Ph2 P(Me)+ derivatives PS or [PMe][BF4 ]2 . Along the series P, PO, PS, and [PMe][BF4 ]2 , the redox potentials shift anodically from E1/2 =-1.89 V to -1.02 V (CH2 Cl2 ). Thus, derivatization of the Ph2 P group allows late-stage modulation of the LUMO-energy level of the DBP. Derivatization also influences the emission properties of the compounds, as PO shows green (521 nm) and [PMe][BF4 ]2 red (622 nm) fluorescence in C6 H6 , while P and PS are dark. With CuBr and AgBr, P forms dimeric [M(µ-Br)]2 complexes [PCu]2 and [PAg]2 , which show pronounced metal-to-ligand charge transfer (MLCT), making P a promising ligand for photocatalysts.

Late-stage derivatization of a (B,O)2-doped perylene.

Regioselective di- and tetrabrominations of the (B,O)2-perylene 1 afford derivatives 2-4. Despite their poor solubility, 2 and 4 could be used in Stille-type coupling reactions to introduce two CCMe (5) or four CC(p-C6H4tBu) substituents (6), respectively. The alkynylated derivatives show blue-green photoluminescence with appreciable quantum efficiencies.

Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory.

Polycyclic aromatic hydrocarbons (PAHs) are prominent lead structures for organic optoelectronic materials. This work describes the synthesis of three B,S-doped PAHs with heptacene-type scaffolds via nucleophilic aromatic substitution reactions between fluorinated arylborane precursors and 1,2-(Me3SiS)2C6H4/1,8-diazabicyclo[5.4.0]undec-7-ene (72-92% yield). All compounds contain tricoordinate B atoms at their 7,16-positions, kinetically protected by mesityl (Mes) substituents. PAHs 1/2 feature two/four S atoms at their 5,18-/5,9,14,18-positions; PAH 3 is a 6,8,15,17-tetrafluoro derivative of 2. For comparison, we also prepared the skewed naphtho[2,3-c]pentaphene-type isomer 4. The simultaneous presence of electron-accepting B atoms and electron-donating S atoms results in a redox-ambiphilic behavior; the radical cations [1•]+ and [2•]+ were characterized by electron paramagnetic resonance spectroscopy. Several low-lying charge-transfer states exist, some of which (especially S-to-B and Mes-to-B transitions) compete on the excited-state potential-energy surface. Consistent with the calculated state characters and oscillator strengths, this competition results in a spread of fluorescence quantum yields (2-27%). The optoelectronic properties of 1 change drastically upon addition of Ag+ ions: while the color of 1 in CH2Cl2 changes bathochromically from yellow to red (λmax from 463 to 486 nm; -0.13 eV), the emission band shifts hypsochromically from 606 to 545 nm (+0.23 eV), and the fluorescence quantum yield increases from 12 to 43%. According to titration experiments, higher order adducts [Agn1m]n+ are formed. As a suitable system for modeling Ag+ complexation, our calculations predict a dimer structure (n = m = 2) with Ag2S4 core, approximately linear S-Ag-S fragments, and Ag-Ag interaction. The computed optoelectronic properties of [Ag212]2+ agree well with the experimentally observed ones.

A free boratriptycene-type Lewis superacid.

Bicyclic pyrazabole-bridged ferrocenes with BH groups at their bridgehead positions were prepared from [Li(thf)]2[1,1'-fc(BH3)2] and pyrazole or 3,5-dimethylpyrazole in the presence of Me3SiCl (1 or 1Me, respectively; 1,1'-fc = 1,1'-ferrocenylene); Me3SiH and H2 are released as byproducts. Treatment of 1 or 1Me with 1 eq. of the hydride scavenger [Ph3C][B(C6F5)4] afforded the borenium salts [2][B(C6F5)4] (72%) and [2Me][B(C6F5)4] (77%). According to X-ray crystallography, [2Me]+ contains one trigonal-planar borenium cation, the cyclopentadienyl (Cp) rings of the 1,1'-fc fragment remain parallel to each other, but the Cp-B bond vector is bent out of the Cp plane by an unprecedentedly large dip angle α* of 40.6°. The Fe⋯B(sp2) distance is very short (2.365(4) Å) and the 11B NMR signal of the cationic B(sp2) center is remarkably upfield shifted (23.4 ppm), suggesting a direct Fe(3d) → B(2p) donor-acceptor interaction. Although this interpretation is confirmed by quantum-chemical calculations, the coupling between the associated orbitals corresponds to an energy of only 12 kJ mol-1. Accordingly, both the experimental (e.g., Gutmann-Beckett acceptor number AN = 111) and theoretical assessment (e.g., Et3PO and F--ion affinities) of the Lewis acidity proves that [2]+ is among the strongest boron-based Lewis acids available to date.

Nucleophilic borylation of fluorobenzenes with reduced arylboranes.

Two challenging but rewarding topics in chemical synthesis are C-F-bond activation and the development of B-centered nucleophiles. We have now tackled both subjects simultaneously by forming aryl-B bonds via SNAr-type reactions on fluorobenzenes under mild conditions using Na2[FluBBFlu], Li2[HBFlu], and Li2[Me2DBA] (BFlu = 9-borafluorenyl, Me2DBA = 9,10-dimethyl-9,10-dihydro-9,10-diboraanthracene).

Subvalent mixed SixGey oligomers: (Cl3Si)4Ge and Cl2(Me2EtN)SiGe(SiCl3)2.

(Cl3Si)4Ge (1; 91%) is accessible from GeCl4, the Si2Cl6/[nBu4N]Cl silylation system, and excess SiCl4. A key intermediate step involves Cl- sequestration with AlCl3 in the course of the reaction between the first-formed germanide [(Cl3Si)3Ge]- and SiCl4. The related adduct Cl2(Me2EtN)SiGe(SiCl3)2 (2; quantitative conversion) was prepared either by amine-induced cleavage of 1 or by a bottom-up synthesis starting from GeCl4 and Si2Cl6.

Selective One-Pot Syntheses of Mixed Silicon-Germanium Heteroadamantane Clusters.

Six Gey alloys are emerging materials for modern semiconductor technology. Well-defined model systems of the bulk structures aid in understanding their intrinsic characteristics. Three such model clusters have now been realized in the form of the Six Gey heteroadamantanes [0], [1], and [2] through selective one-pot syntheses starting from Me2 GeCl2 , Si2 Cl6 , and [nBu4 N]Cl. Compound [0] contains six GeMe2 and four SiSiCl3 vertices, whereas one and two of the GeMe2 groups are replaced by SiCl2 moieties in compounds [1] and [2], respectively. Chloride-ion-mediated rearrangement quantitatively converts [2] into [1] at room temperature and finally into [0] at 60 °C, which is not only remarkable in view of the rigidity of these cage structures but also sheds light on the assembly mechanism.

[Cl@Si20H20]-: Parent Siladodecahedrane with Endohedral Chloride Ion.

Fullerenes and diamondoids are at the core of nanoscience. Comparable monodisperse silicon analogues are scarce. Herein, we report the synthesis of the parent siladodecahedrane, which represents the largest Platonic solid. It shares its pattern of pentagonal faces with the smallest fullerene, C20, and its saturated, H-terminated skeleton with diamondoids. Similar to endofullerenes, the silicon cage encapsulates a chloride ion ([Cl@Si20H20]-); similar to diamondoids, its Si-H termini offer a wealth of opportunities for further functionalization. Mere treatment with chloromethanes leads to the perchlorinated cluster [Cl@Si20Cl20]-. Both compounds were characterized by mass spectrometry, X-ray crystallography, NMR spectroscopy, and quantum-chemical calculations. The experimentally determined 35Cl resonances of the endohedral chloride ions are particularly diagnostic to probe the Cl- → Si20 interaction strength as a function of the different surface substituents, as we have proven by high-level computational analyses.

One tool to bring them all: Au-catalyzed synthesis of B,O- and B,N-doped PAHs from boronic and borinic acids.

The isoelectronic replacement of C[double bond, length as m-dash]C bonds with -B[double bond, length as m-dash]N+ bonds in polycyclic aromatic hydrocarbons (PAHs) is a widely used tool to prepare novel optoelectronic materials. Far less well explored are corresponding B,O-doped PAHs, although they have a similarly high application potential. We herein report on the modular synthesis of B,N- and B,O-doped PAHs through the [Au(PPh3)NTf2]-catalyzed 6-endo-dig cyclization of BN-H and BO-H bonds across suitably positioned C[triple bond, length as m-dash]C bonds in the key step. Readily available, easy-to-handle o-alkynylaryl boronic and borinic acids serve as starting materials, which are either cyclized directly or first converted into the corresponding aminoboranes and then cyclized. The reaction even tolerates bulky mesityl substituents on boron, which later kinetically protect the formed B,N/O-PAHs from hydrolysis or oxidation. Our approach is also applicable for the synthesis of rare doubly B,N/O-doped PAHs. Specifically, we prepared 1,2-B,E-naphthalenes and -anthracenes, 1,5-B2-2,6-E2-anthracenes (E = N, O) as well as B,O2-containing and unprecedented B,N,O-containing phenalenyls. Selected examples of these compounds have been structurally characterized by X-ray crystallography; their optoelectronic properties have been studied by cyclic voltammetry, electron spectroscopy, and quantum-chemical calculations. Using a new unsubstituted (B,O)2-perylene as the substrate for late-stage functionalization, we finally show that the introduction of two pinacolatoboryl (Bpin) substituents is possible in high yield and with perfect regioselectivity via an Ir-catalyzed C-H borylation approach.

A Chemiluminescent Tetraaryl Diborane(4) Tetraanion.

Two subvalent, redox-active diborane(4) anions, [3]4- and [3]2- , carrying exceptionally high negative charge densities are reported: Reduction of 9-methoxy-9-borafluorene with Li granules without stirring leads to the crystallization of the B(sp3 )-B(sp2 ) diborane(5) anion salt Li[5]. [5]- contains a 2,2'-biphenyldiyl-bridged B-B core, a chelating 2,2'-biphenyldiyl moiety, and a MeO substituent. Reduction of Li[5] with Na metal gives the Na+ salt of the tetraanion [3]4- in which two doubly reduced 9-borafluorenyl fragments are linked via a B-B single bond. Comproportionation of Li[5] and Na4 [3] quantitatively furnishes the diborane(4) dianion salt Na2 [3], the doubly boron-doped congener of 9,9'-bis(fluorenylidene). Under acid catalysis, Na2 [3] undergoes a formal Stone-Wales rearrangement to yield a dibenzo[g,p]chrysene derivative with B=B core. Na2 [3] shows boron-centered nucleophilicity toward n-butyl chloride. Na4 [3] produces bright blue chemiluminescence when exposed to air.