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1. Infrared Spectroscopic Characterization of Early 4d Transition Metal Carbene Cations, ZrCH ₂ ⁺ and NbCH ₂ ⁺

   https://doi.org/10.1021/acs.jpca.4c03553  

   Armentrout, P B; Lushchikova, Olga V; Schuurman, Jelle L; Nooteboom, Sjoerd; Ghiassee, Maryam; Boles, Georgia C; Bakker, Joost M (August 2024, The Journal of Physical Chemistry A)
2. Observation of Transition‐Metal–Boron Triple Bonds in IrB ₂ O ⁻ and ReB ₂ O ⁻

   https://doi.org/10.1002/anie.202006652  

   Chen, Teng‐Teng; Cheung, Ling Fung; Chen, Wei‐Jia; Cavanagh, Joseph; Wang, Lai‐Sheng (June 2020, Angewandte Chemie International Edition)

   Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal d_π→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB₂O⁻[Bi≡B−B≡O]⁻in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]⁻fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB₂O⁻and ReB₂O⁻and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB₂O⁻has a closed‐shell bent structure (C_s,¹A′) with BO⁻coordinated to an Ir≡B unit, (⁻OB)Ir≡B, whereas ReB₂O⁻is linear (C_∞v,³Σ⁻) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]⁻. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems. 

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3. All-metal σ-antiaromaticity in dimeric cluster anion {[CuGe ₉ Mes] ₂ } ⁴⁻

   https://doi.org/10.1039/D0CC02525A  

   Wang, Zi-Chuan; Tkachenko, Nikolay V.; Qiao, Lei; Matito, Eduard; Muñoz-Castro, Alvaro; Boldyrev, Alexander I.; Sun, Zhong-Ming (June 2020, Chemical Communications)

   In this work, we report a dimeric cluster anion, {[CuGe 9 Mes] 2 } 4− , which was isolated as the [K(2,2,2-crypt)] + salt and characterized by using single-crystal X-ray diffraction and ESI mass spectroscopy. The title cluster represents the first locally σ-antiaromatic compound in the solid state, as well as the first heteroatomic antiaromatic compound. 

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4. Spherical Aromaticity of All‐Metal [Bi@In ₈ Bi ₁₂ ] ^3−/5− Clusters

   https://doi.org/10.1002/chem.201905264  

   Tkachenko, Nikolay V.; Zhang, Xiang‐Wen; Qiao, Lei; Shu, Cong‐Cong; Steglenko, Dmitry; Muñoz‐Castro, Alvaro; Sun, Zhong‐Ming; Boldyrev, Alexander I. (January 2020, Chemistry – A European Journal)
5. High‐Resolution Photoelectron Imaging of IrB ₃ ⁻ : Observation of a π‐Aromatic B ₃ ⁺ Ring Coordinated to a Transition Metal

   https://doi.org/10.1002/anie.201902406  

   Czekner, Joseph; Cheung, Ling Fung; Kocheril, G. Stephen; Kulichenko, Maksim; Boldyrev, Alexander I.; Wang, Lai‐Sheng (May 2019, Angewandte Chemie International Edition)

   Abstract In a high‐resolution photoelectron imaging and theoretical study of the IrB₃⁻cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B₃ring coordinated with the Ir atom. The isomer with the higher EA consists of a B₃ring with a bridge‐bonded Ir atom (C_s,²A′), and the second isomer features a tetrahedral structure (C_3v,²A₁). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutralC_3visomer involves significant covalent Ir−B bonding and weak ionic bonding with charge transfer from B₃to Ir, and can be viewed as an Ir–(η³‐B₃⁺) complex. This study provides the first example of a boron‐to‐metal charge‐transfer complex and evidence of a π‐aromatic B₃⁺ring coordinated to a transition metal. 

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