Full Electron Delocalization across the Cluster in 1,12-bisBMes2-p-carborane Radical Anion.

Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes2)-p-carborane (B2pCab) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the p-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes2 LUMO. Unlike dianions of other C2B10H12 carboranes, which rearrange to a nido-form, two-electron reduction of B2pCab leads to a rearrangement into a basket-shaped intermediate.

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes.

A cyclic alkyl(amino)carbene (CAAC)-stabilized 1,4-diborabenzene (DBB, 1) reacts with the group 10 precursor [Ni(CO)4] to yield the DBB pogo-stick complex [(η6-DBB)Ni(CO)] (2) as a dark-green crystalline solid. The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong π-donor properties of the DBB ligand. The reaction of 1 with [M(nbe)2] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(η6-DBB)M(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S0→S1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (dxz or dyz) to a d orbital located in the xy plane (dxy or dx2-y2), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2π* orbital destabilizes the DBB···Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe(CO)5] to yield the doubly CO-bridged M(0)→Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn-H addition with Ph3SnH to yield the corresponding Pt(II) stannyl hydride, [(η6-DBB)PtH(SnPh3)] (5).

Structure and Electronics of a Series of CAAC-Stabilized Diboron-Doped Acenes from 1,4-Diboranaphthalene to 6,13-Diborapentacene.

This combined experimental and theoretical study examines the influence of acene elongation, boron atom position, and acene substitution pattern on the structure and electronics of cyclic alkyl(amino)carbene (CAAC)-stabilized diboraacenes and presents the first syntheses of neutral diboranaphthalene (DBN) and diborapentacene (DBP). Whereas 2,3-diethyl-substituted 1,4-(CAAC)2-Et2DBN is isolated as a mixture of a planar (structurally characterized) NMR-active conformer and a presumably bent EPR-active conformer, 6,13-(CAAC)2-DBP resembles 9,10-(CAAC)2-DBA (DBA = diboraanthracene), with a highly puckered 6,13-DBP core and a typical biradical EPR signal. Both species are easily reduced to their puckered dianions. DFT calculations confirm that 6,13-(CAAC)2-DBP is only stable in its bent conformation, whereas 1,4-(CAAC)2-Et2DBN exists as both flat closed-shell and bent open-shell biradical conformers, which interchange by thermally activated ethyl and CAAC rotation/diboraacene bending processes. An in-depth computational study of the series of unsubstituted, CAAC-stabilized, symmetrically diboron-doped acenes from 1,4-(CAAC)2-DBN to 6,13-(CAAC)2-DBP was carried out. The results show interesting trends dependent on the position of the boron atoms within the acene framework as well as on the relative orientation of the CAAC ligands, which enable fine-tuning of the electronic and structural features.

Boron Insertion into the N≡N Bond of a Tungsten Dinitrogen Complex.

The 1,3-addition of 1,2-diaryl-1,2-dibromodiboranes (B2Br2Ar2) to trans-[W(N2)2(dppe)2] (dppe = κ2-(Ph2PCH2)2), which is accompanied by a Br-Ar substituent exchange between the two boron atoms, is followed by a spontaneous rearrangement of the resulting tungsten diboranyldiazenido complex to a 2-aza-1,3-diboraallenylimido complex displaying a linear, cumulenic B=N=B moiety. This rearrangement involves the splitting of both the B-B and N=N bonds of the N2B2 ligand, formal insertion of a BAr boranediyl moiety into the N=N bond, and coordination of the remaining BArBr boryl moiety to the terminal nitrogen atom. Density functional theory calculations show that the reaction proceeds via a cyclic NB2 intermediate, followed by dissociation into a tungsten nitrido complex and a linear boryliminoborane, which recombine by adduct formation between the nitrido ligand and the electron-deficient iminoborane boron atom. The linear B=N=B moiety also undergoes facile 1,2-addition of Brønsted acids (HY = HOPh, HSPh, and H2NPh) with concomitant Y-Br substituent exchange at the terminal boron atom, yielding cationic (borylamino)borylimido tungsten complexes.

Electron-Precise Dicationic Tetraboranes: Syntheses, Structures and Rearrangement to an Alkylidene Borate-Borenium Zwitterion and a 1,3-Azaborinine.

Carbene-stabilized symmetrical and unsymmetrical dicationic tetraboranes, featuring an electron-precise tetraborane chain, were synthesized and fully characterized. Reactions of these tetraboranes with reductants/bases give rise to different outcomes according to the conditions employed, including: 1) reduction and rearrangement of the tetraborane chain to give a zwitterionic alkylidene borate-borenium species; 2) cleavage of the tetraborane chain to afford a 1,3-azaborinine; and 3) reduction of the supporting ligands to provide a diamino dipotassium salt. The zwitterionic alkylidene borate-borenium species can be viewed as an analogue of the base-stabilized diborenes. NMR spectroscopy and DFT calculations reveal a highly polarized B-B bond in the zwitterionic alkylidene borate-borenium, in which the formal oxidation states of the boron atoms can be considered as -1 and +2. These results suggest the considerable potential of tetraboranes as synthons for low-valent boron species.

Aromatic 1,2-Azaborinin-1-yls as Electron-Withdrawing Anionic Nitrogen Ligands for Main Group Elements.

The 2-aryl-3,4,5,6-tetraphenyl-1,2-azaborinines 1-EMe3 and 2-EMe3 (E=Si, Sn; aryl=Ph (1), Mes (=2,4,6-trimethylphenyl, 2)) were synthesized by ring-expansion of borole precursors with N3 EMe3 -derived nitrenes. Desilylative hydrolysis of 1- and 2-SiMe3 yielded the corresponding N-protonated azaborinines, which were deprotonated with nBuLi or MN(SiMe3 )2 (M=Na, K) to the corresponding group 1 salts, 1-M and 2-M. While the lithium salts crystallized as monomeric Lewis base adducts, the potassium salts formed coordination polymers or oligomers via intramolecular K⋅⋅⋅aryl π interactions. The reaction of 1-M or 2-M with CO2 yielded N-carboxylate salts, which were derivatized by salt metathesis to methyl and silyl esters. Salt metathesis of 1-M or 2-M with methyl triflate, [Cp*BeCl] (Cp*=C5 Me5 ), BBr2 Ar (Ar=Ph, Mes, 2-thienyl), ECl3 (E=B, Al, Ga) and PX3 (X=Cl, Br) afforded the respective group 2, 13 and 15 1,2-azaborinin-2-yl complexes. Salt metathesis of 1-K with BBr3 resulted not only in N-borylation but also Ph-Br exchange between the endocyclic and exocyclic boron atoms. Solution 11 B NMR data suggest that the 1,2-azaborinin-2-yl ligand is similarly electron-withdrawing to a bromide. In the solid state the endocyclic bond length alternation and the twisting of the C4 BN ring increase with the sterics of the substituents at the boron and nitrogen atoms, respectively. Regression analyses revealed that the downfield shift of the endocyclic 11 B NMR resonances is linearly correlated to both the degree of twisting of the C4 BN ring and the tilt angle of the N-substituent. Calculations indicate that the 1,2-azaborinin-1-yl ligand has no sizeable π-donor ability and that the aromaticity of the ring can be subtly tuned by the electronics of the N-substituent.

Metal-Free Intermolecular C-H Borylation of N-Heterocycles at B-B Multiple Bonds.

Carbene-stabilized diborynes of the form LBBL (L=N-heterocyclic carbene (NHC) or cyclic alkyl(amino)carbene (CAAC)) induce rapid, high yielding, intermolecular ortho-C-H borylation at N-heterocycles at room temperature. A simple pyridyldiborene is formed when an NHC-stabilized diboryne is combined with pyridine, while a CAAC-stabilized diboryne leads to activation of two pyridine molecules to give a tricyclic alkylideneborane, which can be forced to undergo a further H-shift resulting in a zwitterionic, doubly benzo-fused 1,3,2,5-diazadiborinine by heating. Use of the extended N-heteroaromatic quinoline leads to a borylmethyleneborane under mild conditions via an unprecedented boron-carbon exchange process.

Highly Strained Arene-Fused 1,2-Diborete Biradicaloid.

The stepwise reduction of a doubly cyclic alkyl(amino)carbene (CAAC)-stabilized 2,3-bis(dibromoboryl)naphthalene enables the isolation of the corresponding mono- and bis(boryl) radicals (one- and two-electron reduction), a 2π-aromatic 1,2-diborete (four-electron reduction), which shows biradical character in the solid-state EPR spectrum, and its cyclic bis(alkylidene)diboron dianion (six-electron reduction). The X-ray crystallographic analysis of the diborete shows a highly strained and twisted four-membered ring with a formal cis-diborene motif featuring a very elongated B-B double bond. Calculations based on DFT and multireference approaches reveal that the diborete possesses an open-shell singlet biradicaloid ground state, which is slightly energetically preferred to its EPR-active triplet-state congener. The addition of CO to the diborete resulted in B-B bond splitting and the formation of the corresponding closed-shell singlet, doubly Lewis base-stabilized bis(borylene), whereas a twofold γ insertion of phenyl azide generates a 1,3-bis(diazenyl)-1,3,2,4-diazadiboretidine.

Stable Two-Legged Parent Piano-Stool and Mixed Diborabenzene-E4 (E=P, As) Sandwich Complexes of Group 8.

A cyclic alkyl(amino)carbene-stabilized 1,4-diborabenzene (DBB) ligand enables the isolation of 18-electron two-legged parent piano-stool Fe0 and Ru0 complexes, [(η6 -DBB)M(CO)2 ], the ruthenium complex being the first of its kind to be structurally characterized. [(η6 -DBB)Fe(CO)2 ] reacts with E4 (E=P, As) to yield mixed DBB-cyclo-E4 sandwich complexes with planar E4 2- ligands. Computational analyses confirm the strong electron-donating capacity of the DBB ligand and show that the E4 ligand is bound by four equivalent Fe-P σ bonds.

An Unsymmetrical, Cyclic Diborene Based on a Chelating CAAC Ligand and its Small-Molecule Activation and Rearrangement Chemistry.

A one-pot synthesis of a CAAC-stabilized, unsymmetrical, cyclic diborene was achieved via consecutive two-electron reduction steps from an adduct of CAAC and B2 Br4 (SMe2 )2 . Theoretical studies revealed that this diborene has a considerably smaller HOMO-LUMO gap than those of reported NHC- and phosphine-supported diborenes. Complexation of the diborene with [AuCl(PCy3 )] afforded two diborene-AuI π complexes, while reaction with DurBH2 , P4 and a terminal acetylene led to the cleavage of B-H, P-P, and C-C π bonds, respectively. Thermal rearrangement of the diborene gave an electron-rich cyclic alkylideneborane, which readily coordinated to AgI via its B=C double bond.

Diphosphino-Functionalized 1,8-Naphthyridines: a Multifaceted Ligand Platform for Boranes and Diboranes.

A 1,8-naphthyridine diphosphine (NDP) reacts with boron-containing Lewis acids to generate complexes featuring a number of different naphthyridine bonding modes. When exposed to diborane B2 Br4 , NDP underwent self-deprotonation to afford [NDP-B2 Br3 ]Br, an unsymmetrical diborane comprised of four fused rings. The reaction of two equivalents of monoborane BBr3 and NDP in a non-polar solvent provided the simple phosphine-borane adduct [NDP(BBr3 )2 ], which then underwent intramolecular halide abstraction to furnish the salt [NDP-BBr2 ][BBr4 ], featuring a different coordination mode from that of [NDP-B2 Br3 ]Br. Direct deprotonation of NDP by KHMDS or PhCH2 K generates mono- and dipotassium reagents, respectively. The monopotassium reagent reacts with one or half an equivalent of B2 (NMe2 )2 Cl2 to afford NDP-based diboranes with three or four amino substituents.

Synthesis of Complex Boron-Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions.

The reactions of organic azides with diaryl(dihalo)diboranes(4) were explored, resulting in the observation of a number of surprising reactivity patterns. The reaction of phenyl azide with 1,2-diaryl-1,2-dihalodiboranes(4) resulted in the formation of five-membered rings comprising diboryl-triazenes with retention of the boron-boron bond, while the reaction of the peculiar 1,1-di(9-anthryl)-2,2-difluorodiborane(4) with phenyl azide yielded a six-membered ring bearing a diboryl-triazene, whereby the B-B bond was ruptured by the insertion of an arylnitrene-like reactive intermediate. Both types of heterocycles feature unprecedented connectivity patterns and are very rare examples of boryl triazenes beyond the more common 1,2,3-triazolatoboranes. They are also the product of a unique type of aryl migration from a boron center to the phenyl azide γ-nitrogen center. Lastly, the substitution of 1,2-diaryl-1,2-dihalodiboranes(4) with azide groups, using trimethylsilyl azide as the transfer reagent, yielded boryl-tetrazaboroles and diboryldiazadiboretidines (as side-products), invoking the intermediacy of the first N-boryl-substituted iminoboranes, which are BN isosteres of monoborylated alkynes. The synthetic results are complemented with mechanistic proposals derived from quantum-chemical calculations.

Synthesis, Photophysical and Electronic Properties of New Red-to-NIR Emitting Donor-Acceptor Pyrene Derivatives.

We synthesized new pyrene derivatives with strong bis(para-methoxyphenyl)amine donors at the 2,7-positions and n-azaacene acceptors at the K-region of pyrene. The compounds possess a strong intramolecular charge transfer, leading to unusual properties such as emission in the red to NIR region (700 nm), which has not been reported before for monomeric pyrenes. Detailed photophysical studies reveal very long intrinsic lifetimes of >100 ns for the new compounds, which is typical for 2,7-substituted pyrenes but not for K-region substituted pyrenes. The incorporation of strong donors and acceptors leads to very low reduction and oxidation potentials, and spectroelectrochemical studies show that the compounds are on the borderline between localized Robin-Day class-II and delocalized Robin-Day class-III species.

Reactivity of Tetrahalo- and Difluorodiboranes(4) toward Lewis Basic Platinum(0): Bis(boryl), Borylborato, and Doubly Boryl-Bridged Platinum Complexes.

The reaction of the tetrahalodiboranes(4) B2F4, B2Cl4, and B2Br4 with a Lewis basic platinum(0) complex led to the isolation of the cis-bis(difluoroboryl) complex cis-[(Cy3P)2Pt(BF2)2] (1) and the novel borylborato complexes trans-[(Cy3P)2Pt{B(X)-BX3}] (2, X = Cl; 3, X = Br), respectively. The trans influence of the borylborato group was found to be one of the strongest ever observed experimentally. Furthermore, the reactivity of little-explored diaryldifluorodiboranes(4) F2B-BMes2 and the new derivative F2B-BAn2 (An = 9-anthryl) toward a range of platinum(0) complexes was investigated. Reactions with relatively nonbulky platinum(0) complexes led to the formation of unsymmetrical cis-bis(boryl) complexes cis-[(R3P)2Pt(BF2)(BMes2)] (6, R = Me; 7, R = Et) as well as the first example of a fourfold-unsymmetrical bis(boryl) complex, [(Me3P)(Cy3P)Pt(BF2)(BMes2)] (12). The use of a more bulky Pt complex provided access to the unprecedented dinuclear bis(boryl) complexes [{( iPr3P)Pt}2(µ-BF2)(µ-BAr2)] (8, Ar = Mes; 9, Ar = An), which feature two different µ2-bridging boryl ligands.

CAAC-stabilised 9,10-diboraanthracene: an electronically and structurally flexible platform for small-molecule activation and metal complexation.

A biradical cyclic alkyl(amino)carbene-stabilised 9,10-diboraanthracene (DBA) activates small molecules such as hydrogen, phenyl azide or TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) across its two boron atoms, while reactions with [(MeCN)3M(CO)3] (M = Cr, Mo, W) yield the first half-sandwich DBA complexes of the form [(η6-DBA)M(CO)3].

Synthesis, reduction and C-H activation chemistry of azaborinines with redox-active organoboryl substituents.

The 2,3,4,5,6-pentaphenyl-1,2-azaborinin-1-yl (PPAB) potassium complex 1 undergoes facile salt metathesis with 9,10-dibromo-9,10-dihydroboraanthracene (DBABr2), 5-bromodibenzo[b,d]borole (DBBBr), 1-chlorotetraphenylborole (TPBCl) and dibromo(phenyl)borane (BBr2Ph) to yield the corresponding N-borylated azaborinines N-DBABr-PPAB (2, which hydrolyses and dimerises to the oxo-bridged N,N'-O(DBA)2-(PPAB)2, 3), N,N'-DBA-(PPAB)2 (4), N-DBB-PPAB (5), N-PPB-PPAB (7) and N-BBrPh-PPBA (9). Stepwise reduction of 4 yields the corresponding stable radical anion 4˙- and dianion 42-. One-electron reduction of 5 with KC8 yields the purple radical anion 5˙-, which forms a highly insoluble coordination polymer. 5˙- undergoes very slow radical intramolecular ortho-C-H activation at the C4-phenyl substituent of the PPAB moiety, yielding a BN-analogue of the 5,5'-spiro-bi[dibenzoborole] anion, [6]K. Compound 7 cannot be isolated and undergoes spontaneous and diastereoselective 2,5-anti-addition of the ortho-C-H bond of the PPAB C4-phenyl substituent to yield a novel BNB-analogue of the triply fused dihydrocyclopenta[l]phenanthrene cation, compound 8. Finally the one-electron reduction of 9 results in the ortho-C-H activation of the PPAB C4-phenyl substituent at an in situ-generated dicoordinate boryl anion (10), resulting in the formation of a BNB-analogue of 9H-fluorene, the borate 11-. DFT calculations provide a rationale for the diverse C-H activations observed in these reactions.

Stepwise and selective synthesis of chelating, multimetallic and mixed-metal π-diborene complexes.

The reaction of a pyridyl-substituted, doubly Lewis base-stabilised diborene with different amounts of copper(I) precursors led to the formation of the first chelating π-diborene complexes, the first π-diborene complexes in which metals are bound to both faces of the BB bond, and the first mixed-metal π-diborene species.

Cyclic alkyl(amino)iminates (CAAIs) as strong 2σ,4π-electron donor ligands for the stabilisation of boranes and diboranes(4): a synthetic and computational study.

Singly and doubly cyclic alkyl(amino)iminate (CAAI)-substituted boranes and diboranes(4) were synthesised by halosilane elimination between a silylimine and halo(di)borane precursors. 11B NMR-spectroscopic studies show that the CAAI ligand is a much stronger electron donor than amino ligands. X-ray crystallographic analyses reveal that the degree of B-NCAAI double bonding increases with the electron-withdrawing capacity of the other substituents at boron. The C-N-B bond angle displays a great flexibility, ranging from 131° to near-linear 176°, the narrowest angles being observed for NMe2-substituted derivatives and the widest angles for highly sterically demanding substituents. Density functional theory (DFT) calculations on the electronic structures of the anionic CAAI ligand compared to unsaturated and saturated N-heterocyclic iminate (NHI) ligands show that the former is the best σ donor of the three but less π-donating than the unsaturated NHI. Nevertheless, the linear (CAAI)BH2 complex displays somewhat stronger C-N and N-B π bonding than the corresponding ((S)NHI)BH2 complexes.

Boroles from alumoles: accessing boroles with alkyl-substituted backbones via transtrielation.

The alumole Cp3tAlC4Et4 (Cp3t = 1,2,4-tris(tert-butyl)cyclopentadienyl) is reported to be capable of transferring its butadiene moiety to aryl(dihalo)boranes to generate boroles through aluminum-boron exchange. The products feature a rare alkyl-substituted backbone, which, as shown in other examples, often leads to dimerization due to insufficient steric protection of the antiaromatic borole ring. Sterically crowded aryl groups bound to the boron atom are shown to prevent dimerization, allowing access to the first monomeric derivatives of this type. Results from UV-vis spectroscopy, electrochemistry, and DFT calculations reveal that the alkyl substituents cause remarkable modifications in the optical and electronic properties of the boroles compared to their perarylated counterparts.

Spontaneous N2-diboranylation of [W(N2)2(dppe)2] with B2Br4(SMe2)2.

The 1,3-bromoboration of [W(N2)2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) with B2Br4(SMe2)2 in the presence of various Lewis bases L yields diboranyldiazenido complexes, with L coordinating either at the terminal or internal boron atom. The 2 : 1 reaction of [W(N2)2(dppe)2] and B2Br4(SMe2)2 yields a 1,2-bis(diazenido)diborane-bridged ditungsten complex with a fully planar π-conjugated BrWN2B2Br2N2WBr core.