Synthesis, Characterization, and Reactivity of Metalla‐Chalcogenirenium Compounds^†

Abstract

Metalla-chalcogenirenium | Density functional calculations | Metallacycles | P-block cations | AromaticityChalcogenirenium cations, featuring an unsaturated three-membered organic ring, are limited but known to be synthesizable from alkynes with bulky electron-donating groups. Metalla-chalcogenirenium compounds have been synthesized as stable compounds through the reactions of a cyclic metal-carbyne complex-metallapentalyne with PhSCl, PhSeCl or PhTeCl. As a result of the high strain in the three-membered metallacycles, the metalla-chalcogenirenium cations react readily with the base or chloride ions. These reactions furnish a series of unprecedented chalcogenirenium cations with intact M=C bonds. The intrinsic stabilization effect of aromaticity is further elucidated by density functional calculations.

One‐Pot Synthesis of High‐Strained Metal Vinylidene and Metal Carbyne

“…Our previous studies demonstrated the strain-release reactivity of metallacycles based on the fact that the angle strain is partially relieved upon the reactions of MÀ C multiple bonds with nucleophiles or electrophiles. [27][28][29][30]37,[41][42][43][44] However, complex 2 shows unexpected inertness to classic nucleophiles, such as amines, sodium methoxide and sodium thiomethoxide, and even remains unchanged in the presence of sodium borohydride, lithium phenylacetylene or potassium hydroxide.…”

“…However, attaining access to a metal vinylidene within a ring, especially a small ring (less than six‐membered ring), is much difficult due to the linear nature of M=C=C unit. We previously demonstrated that the constraint of M−C multiple bonds when producing metallacycles invokes reactivities and provides opportunities to obtain novel structures by “strain‐release” strategy [21–32] . In the present work, we achieved a ready synthesis of metal vinylidene within a fused five‐membered ring by one‐pot reaction at room temperature (RT) (Scheme 2).…”

“…We previously demonstrated that the constraint of MÀ C multi-ple bonds when producing metallacycles invokes reactivities and provides opportunities to obtain novel structures by "strain-release" strategy. [21][22][23][24][25][26][27][28][29][30][31][32] In the present work, we achieved a ready synthesis of metal vinylidene within a fused fivemembered ring by one-pot reaction at room temperature (RT) (Scheme 2). The two π-systems present in the M=C=C unit in 2 are unconventional and remarkably inert toward both nucleophiles and electrophiles.…”

Bucket Effect to Improve Third‐Order Nonlinear Optical Response on Metal‐Heteroaromatic Compounds

“…[ 13 ] Metal‐heteroaromatics compounds have flourished in recent decades since they were proposed by Hoffmann in 1979. [ 14 ] Representatively, carbolong, a class of metal‐heteroaromatic compounds, has been widely used in various application fields, [ 15‐16 ] including organic catalysis, [ 17‐19 ] photoluminescence, [ 20‐21 ] biomedicine, [ 22 ] and solar cells. [ 23 ] However, the unique π‐conjugated systems of carbolong provide the possibility for third‐order NLO, which remains to be explored.…”

A One‐Pot Strategy for the Synthesis of β‐Substituted Rhoda‐ and Irida‐Carbolong Complexes

“…Four classes of carbolong complexes, namely osma‐, ruthena‐, rhoda‐ and irida‐carbolong complexes, are now available, according to their different metal centers. [ 51 ] Compared to the rich and well‐studied chemistry of group 8 metal‐based carbolong complexes, [ 51‐62 ] the research on those based on group 9 metals is far less. [ 63‐67 ]…”