Synthesis, Reactivity, and Complexation with Fe(0) of a Tight-bite Bis(N-heterocyclic silylene).

The synthesis, reactivity, and complexation with Fe(0) precursor of a tight-bite bis(N-heterocyclic silylene) (bis(NHSi)) ligand 1 are reported. The reaction of 1 with p-toluidine led to the activation of both N-H bonds across Si(II) atoms to afford a four-membered heterocyclic cyclodisilazane 2, with hydride substituents attached to five-coordinate Si atoms. A 1 : 2 reaction of 1 with Fe(CO)5 led to an intriguing dinuclear complex 3 featuring a five-membered (N-Si-Fe-Fe-Si) ring with a Fe-Fe bond distance of 2.6892(13) Å. All compounds (1-3) were thoroughly characterized by various spectroscopic methods and X-ray diffraction studies conclusively established their molecular structures. DFT calculations were carried out to shed light on bonding and energetic aspects in 1-3.

Preparation of a Compound with a SiII -SiIV -SiII Bonding Arrangement.

Herein, we report the synthesis of a rare bis-silylene, 1, in which two SiII atoms are bridged by a SiIV atom. Compound 1 contains an unusual SiII -SiIV -SiII bonding arrangement with SiII -SiIV bond distances of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe0 complex 2 with two unusually long Si-Si bonds (2.4515(8) and 2.4488(10) Å). We have also carried out a detailed computational study to understand the nature of the Si-Si bonds in these compounds. Natural bond orbital (NBO) and energy decomposition analysis-natural orbital for chemical valence (EDA-NOCV) analyses reveal that the Si-Si bonds in 1 and 2 are of an electron-sharing nature.

Stabilization of NH- Group Adjacent to Naked Silicon(II) Atom in Base Stabilized Aminosilylenes.

Aminosilylene, comprising reactive NH- and Si(II) sites next to each other, is an intriguing class of compounds due to its ability to show diverse reactivity. However, stabilizing the reactive NH- group next to the free Si(II) atom is challenging and has not yet been achieved. Herein, we report the first examples of base stabilized free aminosilylenes Ar*NHSi(PhC(Nt Bu)2 ) (1 a) and Mes*NHSi(PhC(Nt Bu)2 ) (1 b) (Ar*=2,6-dibenzhydryl-4-methylphenyl and Mes*=2,4,6-tri-tert-butylphenyl), tolerating a NH- group next to the naked Si(II) atom. Remarkably, 1 a and 1 b exhibited interesting differences in their reactivity upon heating. With 1 a, an intramolecular C(sp3 )-H activation of one of the benzhydryl methine hydrogen atoms to the Si(II) atom produced the five-membered cyclic silazane 2. However, with 1 b, a rare 1,2-hydrogen shift to the Si(II) atom afforded a silanimine 3, with a hydride ligand attached to an unsaturated silicon atom. Further, the coordination capabilities of 1 a were also tested with Ru(II) and Fe(0) precursors. Treatments of 1 a with [Ru(η6 -p-cymene)Cl2 ]2 led to the isolation of a η6 -arene tethered complex [RuCl2 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si-η6 -arene}] (4), whereas with the Fe(CO)5 precursor a Fe(0) complex [Fe(CO)4 {Ar*NHSi(PhC(t BuN)2 )-κ1 -Si}] (5) was obtained. Density functional theory (DFT) calculations were conducted to shed light on the structural, bonding, and energetic aspects in 1-5.

A Neutral Planar Four-Membered Si2B2 2π-Aromatic Ring.

The synthesis of the first inorganic four-membered neutral 2π-aromatic compound 2 is reported. This unique ring has been synthesized from a simple and straightforward reaction of amidinato-silylene with dichlorophenylborane, followed by the reduction with KC8 in THF. Compound 2 has been fully characterized by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy, and mass spectrometry. The computational calculations reveal that the Si2B2 ring is a π-delocalized system resulting from the interaction of pπ orbital of B and Si-N σ* orbitals having pseudo π symmetry. Compound 2 is the first known example of a neutral planar inorganic analogue of cyclobutenyl dication.

Reactivity of Silylene with Gallium- and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products.

Herein, we report a one-pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi-R, (L=PhC(Nt Bu)2 ). The reaction of LSiCl with an equivalent amount of GaI3 in the presence of KC8 leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si→GaI2 -Si(L)→GaI3 (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene. In this Lewis acid-base reaction the oxidation states of the starting materials remain unchanged. The same is valid in the silylene boron adduct formation of L(t Bu)Si-BPhCl2 (2) and L(t Bu)Si-BBr3 (3). This new route provides access to galliumhalosilanes challenging to synthesize by any other method.

Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb.

Herein we report the reduction of R-EX2 (E=P, Sb) with two equivalents of KC8 in the presence of silylene (LSiR; L=PhC(NtBu)2 ) to give Trip-P=SiL(C6 H4 PPh2 ) (1), Ter Ph-P=(tBu)SiL (2) and Ter Ph-Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N-), containing a formal >Si=Sb- double bond. The theoretical calculations suggest that lone pairs on the dicoordinated group-15 centers are stabilized by hyperconjugative interactions resulting in pseudo-Si-P/Si-Sb multiple bonds which are highly reactive as indicated by the high first and second proton affinities.

Coordination and Stabilization of a Lithium Ion with a Silylene.

Herein, we report the stabilization of lithium-ion as the source of lithium to use as a trans-metalation reagent [{PhC(Nt Bu)2 Si(t Bu)Li}2 I(t BuN)2 CPh] (1). The reaction of 3 equivalents of the LSit Bu (L=PhC(Nt Bu)2 ) and lithium iodide at low temperature leads to a silylene stabilized lithium-ion with an additional coordination of amidinate ligand. Compound 1 shows two four membered and one six membered ring as confirmed by QTAIM calculations. Whereas the reaction of the LSiCl with 1.5 equivalents of carbodiimide (CyN)2 C at room temperature affords compound [PhC(Nt Bu)2 Si(Cl)(NCy)2 NCy] (2) with the CN2 SiN2 C skeleton containing silicon as a central atom. Both the compounds were fully characterized by NMR, mass spectrometry, X-ray crystallographic analysis, and quantum mechanical calculations.

[2+4] Cycloaddition Product of an Amidinate Substituted Dialumene with Toluene.

Reduction of LAlI2 (L=PhC(Ni Pr2 C6 H3 )2 ) with two equivalents of KC8 in toluene affords the [2+4]cycloaddition product of a dialumene with toluene. The mechanism for the formation of product complex was investigated using density functional theory (DFT) methods.

Compounds with Alternating Single and Double Bonds of Antimony and Silicon; Isoelectronic to Ethane-1,2-diimine.

We present an approach for preparing chain-type unsaturated molecules with low oxidation state Si(I) and Sb(I) supported by amidinato ligands that exploit to generate heavy analogues of ethane 1,2-diimine. The reduction of antimony dihalide (R-SbCl2) with KC8 in the presence of silylene chloride afforded L─(Cl)Si═Sb─Tip (1) and L(Cl)Si═Sb─TerPh (2), respectively. Compounds 1 and 2 further undergo reduction with KC8 to produce Tip─Sb═LSi─LSi═Sb─Tip (3) and TerPh─Sb═LSi─LSi═Sb─TerPh (4). The solid-state structures and DFT studies show that all compounds have σ-type lone pairs at each Sb atom. It forms a strong pseudo-π-bond with Si. The pseudo-π-bond is formed by the hyperconjugative donation of the π-type lone pair at Sb to the Si-N σ* MO. The quantum mechanical studies indicate that compounds 3 and 4 has delocalized pseudo-π-MOs arising from hyperconjugative interactions. Hence, 1 and 2 can be considered as isoelectronic to imine, while 3 and 4 are isoelectronic to ethane-1,2-diimine. The proton affinity studies indicate that the pseudo-π-bond resulting from the hyperconjugative interaction is more reactive than the σ-type lone pair.

A Neutral Borylene and its Conversion to a Radical by Selective Hydrogen Transfer.

A successful selective reduction of X2B-Tip (Tip = 1,3,5-iPr3-C6H2, X = I, Br) with KC8 and Mg metal, respectively, in the presence of a hybrid ligand (C6H4(PPh2)LSi) leads to a stable low-valent five-membered ring as a boryl radical [C6H4(PPh2)LSiBTip][Br] (1) and neutral borylene [C6H4(PPh2)LSiBTip] (2). Compound 2 reacts with 1,4-cyclohexadiene, resulting in hydrogen abstraction to afford the radical [C6H4(PPh2)LSiB(H)Tip] (3). Quantum chemical studies reveal that compound 1 is a B-centered radical, and compound 2 is a phosphane and silylene stabilized neutral borylene in a trigonal planar environment, whereas compound 3 is an amidinate-centered radical. Although compounds 1 and 2 are stabilized by hyperconjugation and π-conjugation, they display high H-abstraction energy and basicity, respectively.

Geometrically Compelled Silicon(II)/Silicon(IV) Donor-Acceptor Interaction Enables the Enamination of Nitriles.

Discovering new bonding scenarios and subsequently exploring the reactivity contribute substantially to advance the main group element chemistry. Herein, we report on the isolation and characterization of an intriguing class of the hydrido-benzosiloles 2-4. These compounds exhibit a side arm of the amidinatosilylenyl group, featuring unidirectional silicon(II)/silicon(IV) donor-acceptor interaction on account of the geometric constraint. Furthermore, the reactions involving 2-4 with nitriles yield the tricyclic compounds that edge-fused of the Si-heteroimidazolidine-CN2 Si2 , silole-C4 Si, and phenyl-C6 -rings (5-13). These compounds are manifesting a unique reaction that the silicon(II)/silicon(IV) interaction enables the enamination of the α-H-bearing nitriles. The reaction mechanism involved in H-shift under oxidative addition at silylene followed by hydrosilylation of a ketenimine intermediate was revealed by density function theory (DFT) calculations.

One- and Two-Electron Transfer Oxidation of 1,4-Disilabenzene with Formation of Stable Radical Cations and Dications.

Electron-transferable oxidants such as B(C6 F5 )3 /nBuLi, B(C6 F5 )3 /LiB(C6 F5 )4 , B(C6 F5 )3 /LiHBEt3 , Al(C6 F5 )3 /(o-RC6 H4 )AlH2 (R=N(CMe2 CH2 )2 CH2 ), B(C6 F5 )3 /AlEt3 , Al(C6 F5 )3 , Al(C6 F5 )3 /nBuLi, Al(C6 F5 )3 /AlMe3 , (CuC6 F5 )4 , and Ag2 SO4 , respectively were employed for reactions with (L)2 Si2 C4 (SiMe3 )2 (C2 SiMe3 )2 (L=PhC(NtBu)2 , 1). The stable radical cation [1]+. was formed and paired with the anions [nBuB(C6 F5 )3 ]- (in 2), [B(C6 F5 )4 ]- (in 3), [HB(C6 F5 )3 ]- (in 4), [EtB(C6 F5 )3 ]- (in 5), {[(C6 F5 )3 Al]2 (µ-F)]- (in 6), [nBuAl(C6 F5 )3 ]- (in 7), and [Cu(C6 F5 )2 ]- (in 8), respectively. The stable dication [1]2+ was also generated with the anions [EtB(C6 F5 )3 ]- (9) and [MeAl(C6 F5 )3 ]- (10), respectively. In addition, the neutral compound [(L)2 Si2 C4 (SiMe3 )2 (C2 SiMe3 )2 ][µ-O2 S(O)2 ] (11) was obtained. Compounds 2-11 are characterized by UV-vis absorption spectroscopy, X-ray crystallography, and elemental analysis. Compounds 2-8 are analyzed by EPR spectroscopy and compounds 9-11 by NMR spectroscopy. The structure features are discussed on the central Si2 C4 -rings of 1, [1]+. , [1]2+ , and 11, respectively.

A Carbene-Stabilized Boryl-Phosphinidene.

Herein, the synthesis and characterization of the carbene-stabilized boryl phosphinidenes 1-3 are reported. Compounds 1-3 are obtained by reacting Me-cAAC=PK (Me2 -cAAC=dimethyl cyclic(alkyl)(amino)carbene) and dihaloaryl borane in toluene. All three compounds were characterized by X-ray crystallography. Quantum mechanical studies indicated that these compounds have two lone pairs on the P center viz., an σ-type lone pair and a "hidden" π-type lone pair. Hence, these compounds can act as double Lewis bases, and the basicity of the π-type lone pair is higher than the σ-type lone pair.

Insertion Reaction of Me3SiN3 with Bis(germylene).

Herein, we describe the redox reaction of bis(germylene) PhC(NtBu)2Ge-Ge(NtBu)2CPh with different equivalents of Me3SiN3 affording two distinct products. The reaction of Me3SiN3 with bis-germylene in a 1:1 molar ratio results in compound 1 at -78 °C; however, treatment of bis-germylene with a 2.1 equiv of Me3SiN3 at room temperature results in compound 2. The formation of 1 and 2 can be rationalized by two successive 3 + 1 cycloadditions of Me3SiN3 with the germanium center of bis(germylene) and N2 elimination. All of the compounds are well-characterized by various spectroscopic techniques and single-crystal X-ray structural analyses. Density functional theory (DFT) calculations suggest that compound 2 has a dicoordinated nitrogen atom, which is stabilized by hyperconjugative interactions, resulting in pseudo-germylimine moiety. However, the dicoordinated nitrogen atom shows high basicity as indicated by proton affinity values. These are rare examples of isolated products that show insertion as well as simultaneous redox properties of bis(germylene).

Deoxygenating Reduction of CO2 by [Cp*Al]4 to Form a (Al3O2C)2 Cluster Featuring Two Ketene Moieties.

Herein we report that the reaction of the low-valent aluminum(I) species [Cp*Al]4 (Cp* = pentamethylcyclopentadienyl) with CO2 exhibits complete cleavages of the C═O bonds. The deoxygenating reduction reaction of [Cp*Al]4 with CO2 at 120 °C afforded [(Cp*)3Al3O2C(CO)]2 (1), which featured two stacked (Al3O2C)2 units and two C═C═O ketene moieties. Moreover, the isoelectronic analogues of diimine and isothiocyanate with CO2 were also investigated, and the reactions of [Cp*Al]4 with Dipp*-N═C═N-Dipp* and Dipp-C═N═S [Dipp* = 2,6-bis(diphenylmethyl)-4-tert-butylphenyl; Dipp = 2,6-diisopropylphenyl] afforded dialuminylimine (2) and tetrameric [Cp*AlS]4 (3), respectively.

Stable Radical Cation and Dication of a 1,4-Disilabenzene.

The reaction of (LSi:)2 (1; L = PhC(NtBu)2) with 2 equiv of Me3SiC2C2SiMe3 resulted in the formation of (Me3SiC2)2(Me3Si)2C4Si2(L)2 (2). 2 exhibited a one-electron transfer when treated with 1 equiv of [Ph3C]+[B(C6F5)4]- to yield [(Me3SiC2)2(Me3Si)2C4Si2(L)2]·+[B(C6F5)4]- (3) and Ph3CCPh3, respectively. When compound 2 was treated with 2 equiv of AgOSO2CF3 a transfer of two electrons occurred to produce [(Me3SiC2)2(Me3Si)2C4Si2(L)2]2+·2[OSO2CF3]- (4) and elemental silver. The 1,4-disilabenzene 2 is disclosed of an open-shell singlet diradical character, and 3 and 4 are, respectively, the elusive stable radical cation and dication species of the 1,4-disilabenzene (2). Furthermore, 2 reacted with group 16 elements of O, S, and Se by oxidative addition to form (Me3SiC2)2(Me3Si)2C4Si2(L)2(µ-O2) (5) and (Me3SiC2)2(Me3Si)2C4Si2(L)2(µ-E) (E = S (6) and Se (7)), respectively.

1-Aza-2,4-disilabicyclo[1.1.0]butanes with Superelongated C-N σ-Bonds.

Two silylene molecules oxidatively react under formal [1 + 2 + 1]-cycloaddition to the C≡N bond of nitriles to yield 1-aza-2,4-disilabicyclo[1.1.0]butanes (L)(Cl)Si[µ-η1,2-NC(p-RC6H4)]Si(Cl)(L) (L = PhC(NtBu)2, R = CF3 (2), F (3), Cl (4), Br (5)). The strongly folded bicyclic SiCNSi cores in 2-5 feature inverted bridgehead carbon atoms and superelongated C-N bonds [1.745(12) to 1.801(2) Å], exceeding the lengths of C-N single bonds in known silaaziridines by up to 23%. Detailed bonding analysis discloses C-N bonding interactions, sharing far-reaching similarities with the central C-C bond in [1.1.1]propellane.

Donor-Stabilized Antimony(I) and Bismuth(I) Ions: Heavier Valence Isoelectronic Analogues of Carbones.

Isolation of two-coordinate compounds of heavier Group 15 elements in low oxidation state is challenging due to the preferential formation of dimers or oligomers. Herein, we report the first examples of donor-stabilized two-coordinate Sb(I) and Bi(I) ions. The reduction of antimony and bismuth trihalides with KC8 in the presence of cyclic alkyl(amino) carbene (cAAC) afforded Sb(I) and Bi(I) cations in the form of triflate salts [(cAAC)2Sb][OTf] (1) and [(cAAC)2Bi][OTf] (2). Compounds 1 and 2 belong to a new class of acyclic cations of Group 15 with eight valence electrons and are heavier valence isoelectronic analogues of carbones. Both compounds are isolated and well-characterized by NMR spectroscopy, cyclic voltammetry, single-crystal X-ray diffraction, and computational studies.

Synthesis and Coordination Behavior of a New Hybrid Bidentate Ligand with Phosphine and Silylene Donors.

This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2 SiC6 H4 PPh2 (1) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6 H4 PPh2 ) with chlorosilylene (PhC(NtBu)2 SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7, respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9. X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2 ]- . All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.

Selective Route to Stable Silicon-Boron Radicals and Their Corresponding Cations.

Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of Br2BTip (Tip = 2,4,6-iPrC6H2) with KC8 in the presence of LSi-R affords LSi(tBu)-B(Br)Tip (1) and LSi(N(TMS)2)-B(Br)Tip (2) [L = PhC(NtBu)2]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms. 1 and 2 exhibit extraordinary stability to high temperatures under inert conditions in solution and air stability in the solid state. Both radicals have been isolated and fully characterized by electron paramagnetic resonance spectroscopy, SQUID magnetometry, mass spectrometry, cyclic voltammetry, single-crystal X-ray structure analysis, and density functional theory calculations. Moreover, compound 1 exhibits one-electron transfer when treated with 1 equiv of AgSO3CF3 and [Ph3C]+[B(C6F5)4]-, respectively, resulting in the corresponding cations [LSi(tBu)-B(Br)Tip]+[CF3SO3]- (3) and [LSi(tBu)-B(Br)Tip]+[B(C6F5)4]- (4). Compounds 3 and 4 have been characterized with multinuclear NMR and mass spectrometry.