Strained <i>ansa</i> Half-Sandwich Complexes of Ruthenium and Osmium and a Non-Iron Metallopolymer by Ring-Opening Polymerization

Herein we report the first non-iron polymer obtained from an <i>ansa</i> half-sandwich complex. This polymeric organometallic material was obtained from a new disilanediyl-bridged ruthenium complex upon thermally induced ring-opening polymerization (ROP). Additionally, a corresponding distannanediyl-bridged osmium species is reported, the first example of an <i>ansa</i> half-sandwich complex of this element

A Paramagnetic Heterobimetallic Polymer: Synthesis, Reactivity, and Ring-Opening Polymerization of Tin-Bridged Homo- and Heteroleptic Vanadoarenophanes

The synthesis of the first tin-bridged bis­(benzene) vanadium and trovacene sandwich compounds and the investigation of their oxidative addition and insertion behavior are reported. The vanadoarenophanes and the corresponding platinum insertion products were fully characterized including electrochemical and electron paramagnetic resonance (EPR) measurements. Controllable ring-opening polymerization of the heteroleptic tin-bridged [1]­trovacenophane using Karstedt’s catalyst yields a high molecular weight polymer (up to <i>M</i>_n = 89 200 g·mol^–1) composed of d⁵-vanadium metal centers in the main chain, making it a rare example of a spin-carrying macromolecule. Magnetic susceptibility measurements (SQUID) confirm the paramagnetic scaffold with repeating <i>S</i> = 1/2 centers in the main chain and suggest antiferromagnetic interactions between adjacent spin sites (Weiss constant Θ = −2.9 K)

A Paramagnetic Heterobimetallic Polymer: Synthesis, Reactivity, and Ring-Opening Polymerization of Tin-Bridged Homo- and Heteroleptic Vanadoarenophanes

The synthesis of the first tin-bridged bis­(benzene) vanadium and trovacene sandwich compounds and the investigation of their oxidative addition and insertion behavior are reported. The vanadoarenophanes and the corresponding platinum insertion products were fully characterized including electrochemical and electron paramagnetic resonance (EPR) measurements. Controllable ring-opening polymerization of the heteroleptic tin-bridged [1]­trovacenophane using Karstedt’s catalyst yields a high molecular weight polymer (up to <i>M</i>_n = 89 200 g·mol^–1) composed of d⁵-vanadium metal centers in the main chain, making it a rare example of a spin-carrying macromolecule. Magnetic susceptibility measurements (SQUID) confirm the paramagnetic scaffold with repeating <i>S</i> = 1/2 centers in the main chain and suggest antiferromagnetic interactions between adjacent spin sites (Weiss constant Θ = −2.9 K)