Isolable Spirocyclic Silylone: π-Delocalized Spiro[3.3]heptasila-2,6-diylidone.

Strained cyclic tetrylones are important synthons due to various synthetic applications. Connecting two cyclic tetrylone rings through a single shared quaternary group 14 element atom to form a spirocyclic molecule has been unexplored both theoretically and experimentally. The formation of a spirocyclic motif has been a synthetic challenge. In contrast, the reaction of amidinato disilicon(I) 1, (Me3P)2SiCl4, and KC8 afforded π-delocalized spiro[3.3]heptasila-2,6-diylidone2 and tetrasilacyclobutadiene byproducts 3 and 4. Compound 2 is the smallest spirocyclic tetrylone derivative, which is composed of a σ-type lone pair and delocalized π bond in each all-silicon spirocyclic ring. The electronic property is supported by its coordination with a W(CO)5 moiety.

Understanding the Impact of Group 14 Elements on the Reactivity of [1 + 2] Cycloaddition Reaction between a Cyclic (Alkyl)(amino)carbene Analogue with a Group 14 Element and a Heavy Acetylene Molecule.

Computational exploration using the density functional theory framework (M06-2X-D3/def2-TZVP) was undertaken to investigate the [1 + 2] cycloaddition reaction between a five-membered-ring heterocyclic carbene analogue (G14-Rea; G14 = group 14 element) and a heavy acetylene molecule (G14G14-Rea). It was theoretically observed that exclusively Si-Rea, Ge-Rea, and Sn-Rea demonstrate the capacity to participate in the [1 + 2] cycloaddition reaction with the triply bonded SiSi-Rea. In addition, only three heavy acetylenes (SiSi-Rea, GeGe-Rea, and SnSn-Rea) can catalyze the [1 + 2] cycloaddition reaction with Si-Rea. Our theoretical findings elucidated that the reactivity trend observed in these [1 + 2] cycloaddition reactions primarily arise from the deformation energies of the distorted G14G14-Rea. Also, our study reveals that the bonding characteristics of their respective transition states are controlled by the singlet-singlet interaction (donor-acceptor interaction), rather than the triplet-triplet interaction (electron-sharing interaction). Additionally, our work demonstrates that the bonding behavior between G14-Rea and G14G14-Rea is predominantly determined by the filled p-π orbital of G14G14-Rea (HOMO) → the empty perpendicular p-π orbital of G14-Rea (LUMO), rather than the vacant p-π* orbital of G14G14-Rea (LUMO) ← the filled sp2 orbital of G14-Rea (HOMO).

A Digermanium(III) 1,2-Dication Stabilized by Amidinate and cAAC-Phosphinidenide Ligands.

A digermanium(III) 1,2-dication comprises two cationic centers located at two interconnected Ge atoms. The strong Coulombic repulsion between two positively charged germanium cations hinders their bond formation. Balancing these two oppositions was achieved by using amidinate and cyclic (alkyl)amino carbene (cAAC)-phosphinidenide ligands, where an amidinato cAAC-phosphinidenidogermylene complex, [LGeP(cAACMe)] (2, where L = PhC(NtBu)2, cAACMe = :C{C(Me)2CH2C(Me)2NAr}, and Ar = 2,6-iPr2C6H3), underwent one-electron oxidation with a bis(phosphinidene) radical cation, [(cAACMe)P]2•+, to form a digermanium(III) 1,2-dication, [LGeP(cAACMe)]22+, in compound 4.

Tetrakis(N-heterocyclic Carbene)-Diboron(0): Double Single-Electron-Transfer Reactivity.

The use of 1,3,4,5-tetramethylimidazol-2-ylidene (IMe) to coordinate with diatomic B2 species afforded a tetrakis(N-heterocyclic carbene)-diboron(0) [(IMe)2B-B(IMe)2] (2). The singly bonded B2 moiety therein possesses a valence electronic configuration 1σg21πu21πg*2 with four vacant molecular orbitals (1σu*, 2σg, 1πu', 1πg'*) coordinated with IMe. Its unprecedented electronic structure is analogous to the energetically unfavorable planar hydrazine with a D2h symmetry. The two highly reactive πg* antibonding electrons enable double single-electron-transfer (SET) reactivity in small-molecule activation. Compound 2 underwent a double SET reduction with CO2 to form two carbon dioxide radical anions CO2•-, which then reduced pyridine to yield a carboxylated pyridine reductive coupling dianion [O2CNC5(H)5-C5(H)5NCO2]2- and converted compound 2 to the tetrakis(N-heterocyclic carbene)-diborene dication [(IMe)2B═B(IMe)2]2+ (32+). This is a remarkable transition-metal-free SET reduction of CO2 without ultraviolet/visible (UV/vis) light conditions.

Reactivity of the Intramolecular Vicinal Group-13/P- and B/Group-15-Based Frustrate Lewis Pairs with Sulfur Dioxide: Mechanistic Insight from DFT.

The emission of SO2 gas by industrialized societies contributes to the occurrence of acid rain in natural environments. In this study, we put forward a theoretical investigation into the capture reactions of SO2. Our analysis centers on the energy profiles of intramolecular 1,2-cyclohexylene-bridged FLP-associated molecules. We will particularly examine the reactions involving G13/P-based (with G13 denoting Group 13 element) and B/G15-based (with G15 representing Group 15 element) FLP-associated molecules. Except for Tl/P-FLP, B/N-FLP, and B/Bi-FLP, our theoretical examinations indicate that the remaining six FLP-associated molecules, namely G13'/P-FLP (G13' = B, Al, Ga, and In) and B/G15 ' -FLP (G15' = P, As, and Sb), can easily undergo SO2 capture reactions due to their energetic feasibility. Particularly, our theoretical findings suggested that 1,2-cyclohexylene-bridged Al/P-FLP, Ga/P-FLP, B/As-FLP, and B/Sb-FLP are capable of undergoing a reversible reaction and returning to the initial reactant state. Our theoretical evidence indicates that the G13-G15 bond length in the 1,2-cyclohexylene-linked G13/G15-FLP can serve as a basis for evaluating the free activation barrier associated with its reaction with SO2. Two theoretical methods, namely, the frontier molecular orbital theory and the energy decomposition analysis-natural orbitals of chemical valence approach, are utilized to investigate the electronic structure and bonding nature of the reactions under consideration. Moreover, the analyses based on the activation strain model revealed that it is the geometrical deformation energies of G13/G15-FLP, which is the key factor that greatly influences the activation barriers of such SO2 capture reactions. Further, our theoretical computations indicate that such capturing reactions of SO2 by intramolecular 1,2-cyclohexylene-linked G13/G15-based FLP-type molecules obey the Hammond postulate.

Influence of the Element and Substituent Effects on the Reactivity of Catching Reactions of Difluorocarbene by Benzene-Bridged and Group-13/Group-15-Based Frustrated Lewis Pairs.

The trapping reactions of CF2 by benzene-bridged Group-13/P-based and B/Group-15-based frustrated Lewis pairs (FLPs) have been computationally investigated based on density functional theory. Interestingly, our theoretical calculations predict that the capture of CF2 by all five Group-13/P-based FLPs is energetically feasible. However, in the B/Group-15-based FLPs, only the phosphorus-based B/P-FLP can trap CF2 from kinetic and thermodynamical viewpoints. According to the analyses of the activation strain model, it can be known that the atomic radius of the G15 element (Lewis base) of benzene-bridged B/Group-15-FLP plays an important role in controlling the reactivity of the CF2 catching reactions, whereas the atomic radius of the Group-13 center (Lewis acid) does not play a role in influencing the activation barrier of these CF2 catching reactions. Our theoretical findings based on sophisticated methods suggest that the forward bonding is the FLP-to-CF2 interaction, the LP (Group-15-donor) → vacant p-π-orbital (CF2), which was quantitatively proved to be strong in such present CF2 catching reactions. However, the back bonding is the CF2-to-FLP interaction, the empty σ-orbital (Group-13-acceptor) ← sp2-σ-orbital (CF2), which was verified to be relatively weak. Our theoretical pieces of evidence reveal that the stronger electron-donating ability of the substituents is attached to the Lewis basic center and can make the reaction barrier of the benzene-bridged Group-13/Group-15-based FLP-related compound catching CF2 smaller and more exothermic.

Reactivity Analysis of the [2 + 2] Cycloaddition between Group-6 ≡ Group-14 Triple-Bonded Complexes and Acetylene: Insights from Theoretical Studies.

Theoretical examinations of reactivity for the formal [2 + 2] cycloaddition of Me-C≡C-Ph to Group-6(G6)≡Group-14(G14) triple-bonded organometallic complexes have been carried out using the M06-2X-D3/def2-TZVP level of theory. Our theoretical findings suggest that Me-C≡C-Ph can undergo adduct formation with all G6≡Si complexes, resulting in the generation of four-membered ring structures. However, among the W≡Group-14 complex reactants, only W≡Si-based, W≡Ge-based, and W≡Sn-based organometallic molecules are capable of undergoing a [2 + 2] cycloaddition reaction with Me-C≡C-Ph. Based on energy decomposition analysis, our theoretical investigations demonstrate that the bonding mechanism in such [2 + 2] cycloaddition reactions involves the creation of two dative bonds between singlet fragments (the donor-acceptor model), as opposed to two electron-sharing bonds between triplet fragments. In addition, the examinations based on the activation strain model indicate that the activation barrier of the [2 + 2] cycloaddition reaction is predominantly governed by the geometric deformation energy of the two reactants (G6≡G14-Rea and Me-C≡C-Ph). Our research using the M06-2X method shows that the barrier heights of [2 + 2] cycloaddition reactions between Me-C≡C-Ph and G6≡Si-Rea are dependent on the geometric changes occurring in both fragments during the transition states, consistent with Hammond's postulate.

N-Phosphinoamidinato Silylene- and Phosphine-Borylborylene Complexes.

This work describes a straightforward method to synthesize a borylborylene without proceeding via the rearrangement of a diborene. An amidinato amidosilylene [LSiNMe2] (L = PhC(NtBu)2) and PMe3 were reacted with an N-phosphinoamidinato diborane 1 and KC8 to form a stable silylene-borylborylene 2 and a persistent phosphine-borylborylene 3, respectively. Compound 2 is stable as the borylene center is well stabilized by the silylene donor and boryl substituent, whereas compound 3 is unstable in solution due to labile PMe3. The latter was illustrated by reacting compound 3 with Ar'NC (Ar' = 2,6-Me2C6H3), where Ar'NC displaced PMe3 and inserted into the N-phosphinoamidinate ligand and B-B bond to form compound 4.

Diverse Reactions of o-Carborane-Fused Silylenes with C≡E (E = C, P) Triple Bonds.

The reactivities of o-carborane-fused silylenes toward molecules with C≡E (E = C, P) bonds are reported. The reactions of bis(silylene) [(LSi:)C]2B10H10 (1a, L = PhC(NtBu)2) with arylalkynes afforded bis(silylium) carborane adducts 2 and 3, showing a Si(µ-C2)Si structure with an open-cage nido-carborane backbone. In contrast, the reaction of 1a with a phosphaalkyne AdC≡P (Ad = 1-adamantyl) smoothly furnished compound 4, comprising fused CPSi rings with a C=Si double bond and Si-Si single bond, and the related formation mechanism was investigated by DFT calculations. Furthermore, when monosilylene [(LSi:)C]CHB10H10 (1b) was employed to react with AdC≡P, compound 5 was isolated. The structure of 5 features a 1,2,3-triphosphetene core. All products were characterized by NMR spectroscopy and/or X-ray crystallography.

NHC-Silyliumylidene Cation-Catalyzed Hydroboration of Isocyanates with Pinacolborane.

The low-oxidation-state silicon-catalyzed hydroboration of isocyanates with pinacolborane (HBpin) using the NHC-silyliumylidene cation catalyst [(IMe)2SiH]I (1, IMe = :C{N(Me)C(Me)}2) is described. In the catalysis, the Si lone pair electrons activate isocyanates, and the latter react with HBpin to form N-boryl formamides at room temperature. Catalyst 1 further activates N-boryl formamides at 70 °C, the intermediates of which react with HBpin to form N-boryl methylamines and (pinB)2O.

Computational insights into the reactivity for the [2+5] cycloaddition reactions of norbornene-linked group 14 element/P-based and Si/group 15 element-based frustrated Lewis pairs with benzaldehyde.

The element effects of Lewis acid (LA) and Lewis base (LB) on the potential energy surfaces of [2+5] cycloaddition reactions of norbornene-based G14/P-based (G14 = group 14 element) and Si/G15-based (G15 = group 14 element) frustrated Lewis pair (FLP)-type molecules with benzaldehyde were theoretically examined via density functional theory and several sophisticated methods. The theoretical findings indicated that among the above nine norbornene-linked G14/G15-based FLPs, only the Si/N-Rea, Si/P-Rea, and Si/As-Rea FLP-assisted compounds can readily undergo cycloaddition reactions with doubly bonded organic systems from kinetic and thermodynamic viewpoints. The energy decomposition analysis showed that the bonding interactions between the norbornene-based G14/G15-FLPs and benzaldehyde are better described in terms of the singlet-singlet model (donor-acceptor model) rather than the triplet-triplet model (electron-sharing model). In particular, natural orbitals for chemical valence findings revealed that the forward bonding is the lone pair (G15) → p-π*(C) interaction, which is a significantly strong FLP-to-benzaldehyde interaction. However, the back-bonding is the p-π*(G14) ← lone-pair orbital(O) interaction, which is a weak benzaldehyde-to-FLP interaction. The analyses based on the activation strain model showed that the larger the atomic radius of either the G14(LA) or the G15(LB) atom, the greater the G14⋯G15 separation distance in the norbornene-based G14/G15-FLP molecule, the smaller the orbital overlaps between G14/G15-FLP and Ph(H)CO, and the higher the activation barrier during its cycloaddition reaction with benzaldehyde.

Computational insights into CO2 binding reactions by intramolecular geminal group-IV+/phosphorus- and zirconium+/group-15-based frustrated Lewis pairs.

In order to reduce global warming, there is growing interest in the design of frustrated Lewis pair (FLP) molecules for CO2 capture. This research aims to investigate the influence of group IV (M) or group 15 (G15) elements on the reactivity of intramolecular geminal M+/G15-based frustrated Lewis pair (FLP) molecules in CO2 capture. Theoretical findings suggest that M+/P-FLP, Zr+/P-FLP, Zr+/As-FLP, and Zr+/Sb-FLP can readily undergo CO2 capture reactions without difficulty. Furthermore, Zr+/As-FLP and Zr+/Sb-FLP are predicted to undergo reversible CO2 binding reactions. Interestingly, our theoretical results suggest that the M-P bond length in isolated M+/P-FLP can serve as a criterion for assessing the free activation and free reaction energy of CO2 binding. To investigate the physical factors governing the reactivity trends for the capture of CO2 reactions by intramolecular geminal M+/G15-FLP, we employed frontier molecular orbital theory, energy decomposition analysis in conjunction with natural orbitals and chemical valence, and the activation strain model. Our theoretical information can assist experimental chemists in applying key factors in the design and synthesis of novel intramolecular geminal M+/G15-FLP molecules.

The reactivity of the trapping reaction of the benzene-bridged boron/phosphorus-based frustrated Lewis pair with difluorocarbene and its group 14 analogs: A theoretical investigation.

The trapping reactions of carbene analogs G14F2 (G14 = group 14 element) by the benzene-bridged B/P-Rea frustrated Lewis pair (FLPs) molecule are studied using density functional theory (B3LYP-D3(BJ)/def2-TZVP). Our theoretical investigations predict that only the CF2 intermediate rather than other heavy carbene analogs can be trapped by the B/P-Rea FLP-type molecule. Energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) analyses indicate that the bonding nature of the G14F2 catching reactions by the B/P-Rea FLP-type molecule is a donor-acceptor (singlet-singlet) interaction rather than an electron-sharing (triplet-triplet) interaction. Moreover, EDA-NOCV and frontier molecular orbital (FMO) theory findings strongly suggest that the lone pair (LP) (P) → vacant p-π-orbital (G14F2 ) interaction rather than the empty σ-orbital (B) ← sp2 -σ-orbital (G14F2 ) interaction plays a predominant role in establishing its bonding condition during the G14F2 trapping reaction with the B/P-Rea FLP-associated molecule. Our activation strain model findings reveal that the atomic radius of the G14 element of G14F2 plays a key role in determining the activation barrier of the G14F2 trapping reactions by the benzene-bridged B/P-Rea FLP. The valence bond state correlation diagram (VBSCD) model developed by Shaik is used to rationalize the calculated results. The VBSCD findings demonstrate that in the present trapping reactions, the singlet triplet splitting of G14F2 plays a significant role in influencing its reaction barrier and reaction enthalpy. Our theoretical results demonstrate that the relationship between the geometrical parameters of the transition states and the corresponding reaction free energy barriers agrees well with the findings based on the Hammond postulate.

Understanding the Reactivity of Combination Reactions of Intramolecular Geminal Group 13 Element/Phosphorus and Gallium/Group 15 Element Frustrated Lewis Pairs with CS2.

The reactions of CS2 captured by intramolecular geminal G13/P-based (G13 = group 13 elements) and Ga/G15-based (G15 = group 15 elements) frustrated Lewis pairs have been theoretically examined by using density functional theory (DFT) computations. With regard to the nine FLP-related compounds, our DFT calculated results reveal that only Al/P-Rea and Ga/P-Rea can kinetically and thermodynamically precede the energetically feasible combination reactions with CS2 to form the five-membered heterocyclic adducts. Our activation strain model analyses on the nine aforementioned model molecules indicate that the atomic radius of the Lewis acceptor (G13) and the Lewis donor (G15) plays a role in controlling their barrier heights to obtain good orbital overlaps among G13/P-Rea, Ga/G15-Rea, and CS2. Our theoretical observations based on the energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) approach strongly indicate that the donor-acceptor bonding (i.e., singlet-singlet bonding) rather than the electron-sharing bonding (i.e., triplet-triplet bonding) plays a central role in determining the bonding conditions of the transition states, G13/P-TS and Ga/G15-TS. In addition, the theoretical evidence obtained by the frontier molecular orbital theory and EDA-NOCV analyses reveals that the best description for the bonding natures of the combination reactions of intramolecular geminal G13/P-Rea and Ga/G15-Rea with CS2 is the lone pair(G15) → p-π*(C) interaction rather than the p-π*(G13) ← p-π(S) interaction. Moreover, our present DFT computations concerning the calculated structures and corresponding relative energetics of the stationary points connected with the aforementioned sophisticated approaches are in accordance with the Hammond postulate.

Isolation of Silacycles from the Reactions of a Monochlorosilylene LSi(:)Cl (L = PhC(NtBu)2) with Ethynyl Lithium Salts.

The reactions of amidinate silylene chloride LSi(:)Cl (L = PhC(NtBu)2) with TMS- and Ph-ethynyl lithium salts gave rise to silacycles 1 and 4, respectively. The formation of 1 and 4 may undergo cyclo-condensations of transient ethynylsilylene intermidiates and the activation of an amidinate backbone. The distinct structures of 1 and 4 may be derived from the different electronic or steric properties of ethynyl substituents, and their formation mechanisms were investigated by density functional theory (DFT) calculations. Moreover, a sequential reaction of LSi(:)Cl with BH3·SMe2 and TMSC≡CLi as well as a reaction of LSi(:)Cl with TMSC≡CLi under O2 exclusively obtained ethynylsilanes 2 and 3, respectively, which indicated that either blocking a lone pair of a Si(II) atom or oxidizing Si(II) to Si(IV) prevents the further conversion of ethynylsilylenes to silacycle 1. All products were characterized by NMR spectroscopy and X-ray crystallography.

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.

Theoretical Study of the Activation Reaction of a Zr+/P-Based Frustrated Lewis Pair with Carbon Dioxide.

The combination reactions of carbon dioxide with a Zr+/P-based frustrated Lewis pair (FLP) were computationally explored within the density functional theory framework [B3LYP-D3(BJ)/def2-TZVP]. Results showed that these reactions are exothermic, associated with relatively low activation barriers, and proceed concertedly involving Zr+-O and P-C chemical bond formations. Theoretical analysis revealed that the shorter the Zr+···P bond length of the Zr+/P-based FLP, the shorter the stretching O-C bond length of CO2 upon reaction, the larger the ∠OCO bending angle of CO2, the smaller the deformation energy of CO2, the lower the barrier height, and the greater the reactivity between the Zr+/P-based FLP and CO2. According to the energy decomposition analysis-natural orbitals for chemical valence, the bonding natures of their associated transition states are determined by the singlet-singlet interaction (donor-acceptor interaction), not the triplet-triplet interaction (electron-sharing interaction). Moreover, the bonding characteristics between Zr+/P-based FLPs and CO2 are established predominantly by the lone pair orbital(P) → the empty p-π* orbital (CO2) interaction, not the empty d-orbital(Zr+) ← the filled p-π orbital (CO2) interaction. With the use of the activation strain model, theoretical examinations showed that the reactivity trend of such combination reactions is mainly attributed to the deformation energies of the deformed reactants. The relationship between deformed geometrical structures and related activation energies is in good agreement with Hammond's postulate.

A Pyridine-Stabilized N-Phosphinoamidinato N-Heterocyclic Carbene-Diboravinyl Cation: Boron Analogue of Vinyl Cation.

A boron analogue of vinyl cation, pyridine-stabilized N-phosphinoamidinato N-heterocyclic carbene (NHC)-diboravinyl cation 2+ , was synthesized by displacement of bromide in diborene 1 with excess pyridine. Experimental and computational studies showed that the positive charge is mainly at the B-B skeleton with delocalization to the pyridine ligand. One of the main modes of reactivity is through the B=B double bond alongside activation of the pyridine substituent, where the Bpyridine center is the predominant nucleophilic center and the predominant electrophilic center is either the activated pyridine para position or the BNHC center, illustrating the presence of diborene cation A, borylene-borenium cation B and diborene-pyridinium cation C resonance structures in cation 2+ .

A N-Phosphinoamidinato NHC-Diborene Catalyst for Hydroboration.

The use of the N-phosphinoamidinato NHC-diborene catalyst 2 for hydroboration is described. The N-phosphinoamidine tBu2PN(H)C(Ph)═N(2,6-iPr2C6H3) was reacted with nBuLi in Et2O to afford the lithium derivative, which was then treated with B2Br4(SMe2)2 in toluene to form the N-phosphinoamidinate-bridged diborane 1. It was reacted with the N-heterocyclic carbene IMe (:C{N(CH3)C(CH3)}2) and excess potassium graphite at room temperature in toluene to give the N-phosphinoamidinato NHC-diborene compound 2. It can stoichiometrically activate ammonia-borane and carbon dioxide. It also showed catalytic capability. A 2 mol % portion of 2 catalyzed the hydroboration of carbon dioxide (CO2) with pinacolborane (HBpin) in deuterated benzene (C6D6) at 110 °C (conversion >99%), which afforded the methoxyborane [pinBOMe] (yield 97.8%, TOF 33.3 h-1) and the bis(boryl) oxide [(pinB)2O]. In addition, 5 mol % of 2 catalyzed the N-formylation of secondary and primary amines by carbon dioxide and pinacolborane to yield the N-formamides (average yield 91.6%, TOF 25.9 h-1). Moreover, 2 showed chemoselectivity toward catalytic hydroboration of carbonyl compounds. In mechanistic studies, the B═B double bond in compound 2 activated the substrates, the intermediates of which then underwent hydroboration with pinacolborane to yield the products and regenerate catalyst 2.

Amidinatoamidosilylene-Dibromodiborene.

The amidinatoamidosilylene [LSiNMe2] [1; L = PhC(NtBu)2] was reacted with B2Br4(SMe2)2 in toluene at room temperature to form the bis(silylene)tetrabromodiborane [L{Me2N}Si]2B2Br4 (2). It was then reacted with excess KC8 in tetrahydrofuran at room temperature to afford the bis(silylene)dibromodiborene [L{Me2N}Si]2B2Br2 (3).