Correction: Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements.

Correction for 'Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements' by Mian He et al., Chem. Soc. Rev., 2024, https://doi.org/10.1039/D3CS00784G.

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

Carbenes (R2C:), compounds with a divalent carbon atom containing only six valence shell electrons, have evolved into a broader class with the replacement of the carbene carbon or the RC moiety with main group elements, leading to the creation of main group carbene analogues. These analogues, mirroring the electronic structure of carbenes (a lone pair of electrons and an empty orbital), demonstrate unique reactivity. Over the last three decades, this area has seen substantial advancements, paralleling the innovations in carbene chemistry. Recent studies have revealed a spectrum of unique carbene analogues, such as monocoordinate aluminylenes, nitrenes, and bismuthinidenes, notable for their extraordinary properties and diverse reactivity, offering promising applications in small molecule activation. This review delves into the isolable main group carbene analogues that are in the forefront from 2010 and beyond, spanning elements from group 13 (B, Al, Ga, In, and Tl), group 14 (Si, Ge, Sn, and Pb) and group 15 (N, P, As, Sb, and Bi). Specifically, this review focuses on the potential amphiphilic species that possess both lone pairs of electrons and vacant orbitals. We detail their comprehensive synthesis and stabilization strategies, outlining the reactivity arising from their distinct structural characteristics.

Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile.

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.

Probing the Electron Accepting Ability of Phosphaphenalenes.

Phosphaphenalenes, extended π conjugates with the incorporation of phosphorus, are attractive avenues towards molecular materials for the applications in organic electronics, but their electron accepting ability have not been investigated. In this study, we present systematic studies on the reductive behavior of a representative phosphaphenalene and its oxide by chemical and electrochemical methods. The chemical reduction of the phosphaphenalene by alkali metals reveals the facile P‒C bond cleavage to form phosphaphenalenide anion, which functions as a transfer block for structure modification on the phosphorus atom. In contrast, the pentavalent P-oxide reacts with one or two equivalents of elemental sodium to form stable radical anion and dianion salts, respectively.

BN Analogue of Butadiyne: A Platform for Dinitrogen Release and Reduction.

Exploration of the metallomimetic chemistry of main group elements is of the utmost importance from the perspective of both fundamental research and potential applications. Here, we report the synthesis, bonding analysis, and reactivities of an isolable diiminoborane, Mes*B≡N─N≡BMes* (Mes* = 2,4,6-tri-tert-butylphenyl) (1), a BN analogue of butadiyne. This species is characterized by a conjugated B≡N─N≡B moiety, a structural feature that enables the controlled release of N2 when it is exposed to organic nitriles. Furthermore, the N2 unit in 1 could be reduced to an ammonium salt via cleavage of the BN triple bond. Our work shows a rare example of an unsaturated BN system, serving as a platform for both the release and reduction of N2. This discovery opens new pathways and holds substantial influence on the future design of functional main group N2 species.

Utilization of a Tris(carbene)borate Ligand for Umpolung Reactivity of a Nucleophilic Tin(II) Cation Salt.

We show that a tris(carbene)borate (TCB) ligand, namely [PhB(tBuIm)3]- ([PhB(tBuIm)3]- = phenyltris(3-tert-butylimidazol-2-ylidene)borato), is capable of stabilizing an unprecedented nucleophilic Sn(II) cation salt. Unlike known Sn(II) cations, the strong electron-donating ability of [PhB(tBuIm)3]- makes the cationic tin atom electron-rich, σ-donating yet slightly π-accepting, which allows for the ensuing facile oxidation with o-chloranil and S8 as well as coordination with coinage metals. The former oxidations give the Sn(IV) cation salts, while the latter reactions produce the metal complexes. The electronic structures of these species are thoroughly probed by quantum chemical computations. These results uncover an added role for TCB ligands in isolating unprecedented p-block species.

Derivatization of an Alkylideneborane with B═C Bond Cleavage.

We present the synthesis, structural characterization, and reactivity of alkylideneborane 2, supported by π-donating N-heterocyclic imino and σ-donating N-heterocyclic carbene (NHC) ligands. The incorporation of these ligands effectively weakens the B═C bond strength, leading to enhanced reactivity. Consequently, selective cleavage of the B═C bond can be achieved using pyridine-N-oxide, sulfur, and selenium, resulting in the formation of 1,3-dioxa-2,4-diboretane 3, thioxoborane 4, and selenoborane 5, respectively. Furthermore, intriguing B═C bond insertions with CO2 and CS2 are observed, affording zwitterionic borenium/fluorenide 6 and dithiaboretane 7. The former species 6 is readily converted to transient oxoborane and imidazolium enolate, showcasing the bora-Wittig reaction of alkylideneborane. This investigation highlights the potential of alkylideneborane as a versatile building block for synthesizing novel organoboron compounds through unconventional transformations.

Unveiling Hetero-Enyne Reactivity of Aryliminoboranes: Dearomative Hetero-Diels-Alder-Like Reactions.

Being isoelectronic with alkynes, iminoboranes with a polar B≡N triple bond have been exclusively investigated as a potent 1,2-dipole in synthetic chemistry. Herein, we disclose the unprecedented reactivity of aryliminoboranes via the BNCC π conjugation, namely hetero-enyne behavior. This allows for facile dearomative Diels-Alder-like reactions of aryliminoboranes with aldehydes. This cycloaddition features mild conditions, is catalyst-free, and has a broad substrate scope and good functional group tolerance. Kinetic and computational studies reveal its second-order reaction and concerted cyclization mechanism. This report unveils new synthetic application of iminoboranes beyond their classical reaction patterns.

Synthesis of Cationic Silaamidinate Germylenes and Stannylenes and the Catalytic Application for Hydroboration of Pyridines.

The N-heterocyclic germylenes and stannylenes LSi(NAr)2EX (L = PhC(NtBu)2, Ar = 2,6-iPr2C6H3; E = Ge, Sn; X = Cl, CF3SO3, BPh4) supported by the bulky silaamidinate ligand [LSi(NAr)2]- have been synthesized and fully characterized. The germylene triflate LSi(NAr)2GeOTf (3b) and dimeric borate [LSi(NAr)2Ge]2ClBPh4 (3a) enabled highly regio- and chemoselective catalytic hydroboration of pyridines and may represent the most active catalytic system for the transformation. DFT calculations disclosed that the cationic germylene [LSi(NAr)2Ge]+ with a low-lying LUMO energy initiated the catalytic process. In contrast, the analogous amidinate germylene triflates are almost inactive, indicating the silaamidinate ligand is essential for the stabilization of cationic species.

A stable rhodium-coordinated carbene with a σ0π2 electronic configuration.

Isolable singlet carbenes have universally adopted a σ2π0 electronic state, making them σ-donors and π-acceptors. We present a rhodium-coordinated, cationic cyclic diphosphinocarbene with a σ0π2 ground state configuration. Nuclear magnetic resonance spectroscopy studies show a carbene carbon chemical shift below -30.0 parts per million. X-ray crystallography reveals a planar RhP2C configuration. Quantum chemical calculations rationalize how σ-electron delocalization/donation and π-electron negative hyperconjugation together stabilize the formally vacant σ orbital and the filled π orbital at the carbene center. In contrast to traditional carbene counterparts this carbene can undergo synthetic transformations with both a Lewis base and a silver salt, producing a Lewis acid/base adduct and a silver π-complex, respectively. Exhibiting ambiphilic reactivity, it can also form a ketenimine through reaction with an isocyanide.

A crystalline stannyne.

The synthesis of heteronuclear alkyne analogues incorporating heavier group 14 elements (R1-C≡E-R2, E = Si, Ge, Sn, Pb) has posed a long-standing challenge. Neutral silynes (R1-C≡Si(L)-R2) and germynes (R1-C≡Ge(L)-R2) stabilized by a Lewis base have achieved sufficient stability for structural characterization at low temperatures. Here we show the isolation of a base-free stannyne (R1-C≡Sn-R2) at room temperature, achieved through the strategic use of a bulky cyclic phosphino ligand in combination with a bulky terphenyl substituent. Despite an allenic structure with strong delocalization of π-electrons, this compound exhibits adjacent ambiphilic carbon and tin centres, forming a carbon-tin multiple bond with ionic character. The stannyne demonstrates reactivity similar to carbenes or stannylenes, reacting with 1-adamantyl isocyanide and 2,3-dimethyl-1,3-butadiene. Additionally, its carbon-tin bond can be saturated by Et3N·HCl or cleaved by isopropyl isocyanate.

Utilizing bis(imino)dihydroacridanide pincer ligands in p-block chemistry: synthesis and catalysis of an antimony monocation salt.

We present the synthesis and characterization of an Sb(III) monocation salt stabilized by a bulky bis(imino)dihydroacridanide pincer ligand. The Lewis acidity of the Sb cation is quantified using the Guttmann-Beckett method and confirmed by its reaction with 4-dimethylaminopyridine, which forms a Lewis acid-base adduct. This Sb cation exhibits catalytic activity in the cyanosilylation of arylketones. The electronic structure of the Sb cation as well as the mechanism of the catalytic transformation are explored by density functional theory computations.

Structure and reactivity studies of the aluminum analogue of Piers' borane [HAl(C6F5)2]3.

The aluminum analogue of Piers' borane, [HAl(C6F5)2]31, is prepared on a gram-scale. Density functional theory (DFT) calculations reveal 1 has a higher fluoride ion affinity (FIA) than Piers' borane, while the Al-H moiety proved to be a strong hydride donor, reacting with alcohol and terminal alkyne to give the corresponding dehydrogenative products 3 and 4. Hydroalumination product 5 was prepared via reaction of 1 with aldehyde. In addition, 1 catalyzes the hydrosilylation of alkynes and alkenes.

Synthesis and reactivity of a µ-1,2-dinitrogen dinickel(II) complex with a C-H activated silaamidinate pincer ligand.

Reaction of the silaamidinate nickel bromide LSi(NAr)2NiBr2Li(thf)(OEt2) (L = PhC(NtBu)2, Ar = 2,6-iPr2C6H3, 1) with NaHBEt3 led to intramolecular C-H activation with the formation of the µ-1,2-dinitrogen dinickel pincer complex [LSi(NAr)(NAr)Ni]2(µ-1,2-N2) (Ar = 2-C(CH3)2-6-iPrC6H3, 2). Single-crystal X-ray diffraction analysis of 2 disclosed a square planar Ni(II) atom bridged by N2. Reaction of 2 with carbon monoxide and 2,6-dimethylphenyl isocyanide yielded square planar carbonyl and isocyanide complexes 3 and 4 with release of N2. These results provide new approaches for the coordination of N2 with nickel(II) species.

Planar Polycyclic Oxaphosphoranes Incorporating a Benzophosphole Unit.

A facile method to synthesize quaternized benzophospholes on gram scale was reported, and the products were isolated by simple filtration. During this research, a series of σ5-oxaphosphoranes incorporating polycyclic aromatic hydrocarbons (PAHs) were obtained. The grafting of α-phenolate groups on the phosphorus center enhances the coplanarity of the system.

A 3-dimensional spiro-functionalized platinum(II) complex to suppress intermolecular π-π and Pt···Pt supramolecular interactions for a high-performance electrophosphorescent device.

A 3-D platinum(II)-based spirometal complex has been designed and synthesized to suppress aggregation and excimer emission. A prototype phosphorescent organic light-emitting device exhibits the high-performance orange emission with an external quantum efficiency of up to 5.2%.