Inorganometallic allenes [(Mn(η⁵-C₅H₅)(CO)₂)₂(μ-E)] (E = Si–Pb): bis-allylic anionic delocalisation similar to organometallic allene but differential σ-donation and π-backdonation

Abstract

The chemistry of heavy group-14 tetrel atoms is known to diverge from that of the lighter congener carbon. Here, we report the structure and bonding in inorganometallic allenes [(Mn(η5-C5H5)(CO)2)2(μ-E)] (E...

A Lead-μ2-Tetrylide Complex with Osmium(IV) Terminal Components

“…The optimized geometry matches the X-ray structure quite well, in particular the Pb–Os bond lengths (2.60 Å). Inspection of the occupied molecular orbitals involving the metal atoms (Figure ) resembles that of the complex (η 5 -C 5 H 5 )(CO) 2 MnPbMn(CO) 2 (η 5 -C 5 H 5 ) …”

“…The strength of the Mn–E bond decreases down the group and is accompanied by a lower contribution of the E atom ns valence orbital to the bond. This atom acts as σ donor and π acceptor, according to the Dewar–Chatt–Duncanson bonding model . On the basis of this feature of the heavier atoms of Group 14, we reasoned that the terminal L n M components of μ 2 -tetrylide complexes linked by such atoms should not necessarily carry a low-valent metal center; on the contrary, they would exhibit greater stability with terminal components of high-valence metallic centers.…”