Boron-heteroelement (B–E; E = Al, C, Si, Ge, N, P, As, Bi, O, S, Se, Te) multiply bonded compounds: Recent advances

Borthakur, Rosmita; Chandrasekhar, Vadapalli

doi:10.1016/j.ccr.2020.213647

Cited by 25 publications

(18 citation statements)

References 208 publications

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“…1.534 Å) and now within the range of true double bonds for tricoordinate boron. 39,40 In 6-Li, the two lithium cations, one positioned above and one below the fused diboracarbocycle, are each stabilized by one THF ligand and display π interactions with the B�C CAAC double bonds, the CAAC nitrogen atoms, and the boron-bound naphthalene C1�C2 bond. Compound 6-K proved to be extremely airsensitive, such that crystals began to decompose during selection (in a glovebox), resulting in poor-quality diffraction data.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Highly Strained Arene-Fused 1,2-Diborete Biradicaloid

et al. 2022

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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.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Highly Strained Arene-Fused 1,2-Diborete Biradicaloid

et al. 2022

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“…However, the B–M bond lengths vary in a wide range, depending on the ligands and the R group 11 . Since the syntheses of the first transition-metal borylene complexes 12 , 13 , considerable progresses have been achieved in this area 14 – 24 . Boron-metal triple-bond characters were first suggested in [(OC) 5 CrBSiH 3 ] with the B–Cr bond length of 1.871 Å 25 , slightly shorter than the B=Cr double-bond length of 1.89 Å derived from Pyykkö’s covalent radii 26 .…”

Section: Introductionmentioning

confidence: 99%

“…Compared with the transition-metal-boron multiple-bond complexes, compounds with multiple bonding between boron and main-group metal elements are rare 24 , even though multiple bonds of boron with light main-group elements are common. This is understandable because main-group metal elements have valence ns and np orbitals with large differences in orbital radii, decreasing the hybridization of these orbitals and making it difficult for heavy elements to form strong multiple bonds.…”

Section: Introductionmentioning

confidence: 99%

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Boron-lead multiple bonds in the PbB2O– and PbB3O2– clusters

Chen

et al. 2022

Commun Chem

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Despite its electron deficiency, boron can form multiple bonds with a variety of elements. However, multiple bonds between boron and main-group metal elements are relatively rare. Here we report the observation of boron-lead multiple bonds in PbB2O– and PbB3O2–, which are produced and characterized in a cluster beam. PbB2O– is found to have an open-shell linear structure, in which the bond order of B☱Pb is 2.5, while the closed-shell [Pb≡B–B≡O]2– contains a B≡Pb triple bond. PbB3O2– is shown to have a Y-shaped structure with a terminal B = Pb double bond coordinated by two boronyl ligands. Comparison between [Pb≡B–B≡O]2–/[Pb=B(B≡O)2]– and the isoelectronic [Pb≡B–C≡O]–/[Pb=B(C≡O)2]+ carbonyl counterparts further reveals transition-metal-like behaviors for the central B atoms. Additional theoretical studies show that Ge and Sn can form similar boron species as Pb, suggesting the possibilities to synthesize new compounds containing multiple boron bonds with heavy group-14 elements.

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“…Heavier main group element-element multiple bond systems are no longer lab curiosities and tremendous effort has been devoted to establish new bonding patterns and to utilize the transition-metal like reactivity of these systems in terms of small molecule activation and functionalization. [1][2][3][4][5][6][7][8][9][10][11] Our group is interested in E 13 -E 15 multiple bond systems, 12 which are the iso-valent electronic heavier analogs of C-C multiple bond systems and have been proposed as intermediates in Metal-Organic Chemical Vapour Deposition (MOCVD) processes, which are based on utilizing molecular single-source E 13 -E 15 precursors. 13,14 The synthesis of E 13 -E 15 multiple bonds is challenging due to adjacent Lewis acidic E 13 and Lewis basic E 15 atoms, resulting in a tendency to oligomerize.…”

Section: Introductionmentioning

confidence: 99%