Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements

He, Mian; Hu, Chaopeng; Wei, Rui; Wang, Xin-Feng; Liu, Liu Leo

doi:10.1039/d3cs00784g

Cited by 8 publications

(3 citation statements)

References 434 publications

(705 reference statements)

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“…These analogs exhibit notable differences from their lighter organic counterparts in terms of stability, bonding scenario, and chemical behavior, largely attributable to the reluctance of heavier elements to engage in s/p hybridization . These distinctions have propelled them into the forefront of synthetic chemistry, where they serve as valuable tools for the innovation of unique species and the development of catalytic methodologies. − …”

Section: Introductionmentioning

confidence: 99%

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile

Li,

Wang,

et al. 2024

J. Am. Chem. Soc.

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Phosphagermylenylidenes (R–PGe), as heavier analogs of isonitriles, whether in their free state or as complexes with a Lewis base, have not been previously identified as isolable entities. In this study, we report the synthesis of a stable monomeric phosphagermylenylidene within the coordination sphere of a Lewis base under ambient conditions. This species was synthesized by Lewis base-induced dedimerization of a cyclic phosphagermylenylidene dimer or via Me3SiCl elimination from a phosphinochlorogermylene framework. The deliberate integration of a bulky, electropositive N-heterocyclic boryl group at the phosphorus site, combined with coordination stabilization by a cyclic (alkyl)(amino)carbene at the low-valent germanium site, effectively mitigated its natural tendency toward oligomerization. Structural analyses and theoretical calculations have demonstrated that this unprecedented species features a PGe double bond, characterized by conventional electron-sharing π and σ bonds, complemented by lone pairs at both the phosphorus and germanium atoms. Preliminary reactivity studies show that this base-stabilized phosphagermylenylidene demonstrates facile release of ligands at the Ge atom, coordination to silver through the lone pair on P, and versatile reactivity including both (cyclo)addition and cleavage of the PGe double bond.

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Section: Introductionmentioning

confidence: 99%

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile

Li,

Wang,

et al. 2024

J. Am. Chem. Soc.

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“…Over recent decades, main-group chemistry has seen considerable advancements, particularly with compounds in low oxidation states, − such as group 13 metallylenes, − tetrylenes, − and pnictinidenes. − These compounds exhibit a broad spectrum of reactivity in small molecule activation and catalysis, , featuring energetically accessible electron pairs and empty orbitals that synergistically activate substrates, mimicking the reactions typically observed in transition metal complexes, such as oxidative addition (OA) . However, these reactions generally yield thermodynamically more stable oxidation products, posing significant challenges in regenerating the low-valent main-group reactants, thereby impeding the establishment of redox catalytic cycles.…”

Section: Introductionmentioning

confidence: 99%

Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling

Huang,

Li,

Zhang

et al. 2024

J. Am. Chem. Soc.

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The stibinidene ArSb I (Ar = [2, 2 -C 6 H 3 ], 1) reacts with S 2 Tol 2 (Tol = p-tolyl) to form ArSb III (STol) 2 (2), which upon treatment with pinacolborane, regenerates 1. These processes unveil an unprecedented antimony redox catalysis involving Sb(I)/Sb(III) cycling for the hydroboration of organic disulfides. Elementary reaction studies and density functional theory calculations support that the catalysis mimics transition metal processes, proceeding through oxidative addition, ligand metathesis, and reductive elimination. The thiophenols and sulfidoborates generated from the hydroboration of disulfides react in situ with α,β-unsaturated carbonyl compounds with the assistance of 1 as a base catalyst. These tandem reactions establish a one-pot synthetic method for β-sulfido carbonyl compounds, in which a stibinidene functions as a redox catalyst and a base catalyst successively, illustrating the versatility and efficiency of antimony catalysis in organic synthesis.

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“…III), we identified the Nheterocyclic boryloxy (NHBO) ligand, OB{(NDippCH) 2 }, as possessing these features-in particular a highly electronegative X-substituent to stabilize the HOMO of EX 2 À anion (which has EÀ X σ* character). [3,38,39] The incorporation of NHBO substituents has been shown to result in wide HOMO-LUMO gaps (e.g., 5.4 eV for [Si{OB(NDippCH) 2 } 2 ] and 4.3 eV for III) primarily due to the presence of a very low-lying HOMO. The HOMO energies of N,N-ligated aluminyls lie in the range À 0.89 to À 0.97 eV, whereas that of NHBO-aluminyl III is À 2.77 eV.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Isolation, and Reactivity Studies of ‘Naked’ Acyclic Gallyl and Indyl Anions

Sarkar,

Vasko,

Gluharev

et al. 2024

Angewandte Chemie

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By exploiting the electronic capabilities of the N‐heterocyclic boryloxy (NHBO) ligand, we have synthesized ‘naked’ acyclic gallyl [Ga{OB(NDippCH)2}2]− and indyl [In{OB(NDippCH)2}2]− anions (as their [K(2.2.2‐crypt)]+ salts) through K+ abstraction from [KGa{OB(NDippCH)2}2] and [KIn{OB(NDippCH)2}2] using 2.2.2‐crypt. These systems represent the first O‐ligated gallyl/indyl systems, are ultimately accessed from cyclopentadienyl GaI/InI precursors by substitution chemistry, and display nucleophilic reactivity which is strongly influenced by the presence (or otherwise) of the K+ counterion.

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Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements

Abstract: This review provides an overview of main group carbene analogues, covering recent advancements, synthesis strategies, and the diverse reactivity of elements in groups 13–15 based on their structural characteristics.

Cited by 8 publications

References 434 publications

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile

Antimony Redox Catalysis: Hydroboration of Disulfides through Unique Sb(I)/Sb(III) Redox Cycling

Synthesis, Isolation, and Reactivity Studies of ‘Naked’ Acyclic Gallyl and Indyl Anions

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