Synthesis and Characterization of Rhodium Complexes with Phosphine-Stabilized Germylenes

Abstract

The reaction of phosphine-stabilized germylenes (1a,b) with dimer complex [Rh(2)(μ-Cl)(2)(COD)(2)] leads to the corresponding phosphine-germylene-Rh(I) complexes (2a,b). Interestingly, the stability of these complexes depends strongly on the nature of the substituent of the germylene fragment. Indeed, the complex (2a) with the chloro-germylene ligand isomerizes into a metallacycle rhodium complex (3a) via germylene insertion into the Rh-Cl bond, while the complex with the phenyl-substituted germylene (2b) was isolated and represents the first stable Rh(I)-germylene complex with a Rh-Cl bond.

A Stable Heterocyclic Amino(phosphanylidene‐σ4‐phosphorane) Germylene

“…The structure of 2 was unambiguously confirmed by an X‐ray diffraction analysis (Figure ) . The molecular structure of 2 is similar to previously reported structures of phosphine‐stabilized germylenes …”

Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity

“…Base‐stabilized tetrylenes were studied intensively and in these inter‐ or intramolecular base adducts the electrophilicity of the Group 14 element is much less pronounced, whereas reactions as a strong nucleophile are well known for these molecules . Therefore, it is not surprising that base‐stabilized tetrylenes exhibit a widespread coordination chemistry and are also prone to oxidative additions . We have studied the reactivity of cyclic intramolecular σ‐donor‐stabilized stannylenes in dependency on the ring size .…”

A simple method for the determination of the Tolman electronic parameter of different phosphorus containing ligands, by means of the average local ionization energy

“…[1] The simple computational and qualitative methodology (R 2 =0.91 correlated with Tolman's original values) proposed in this work, is intrinsic for each molecule (it is independent of the selected metal center) and can easily be applied to new monodentate phosphines or phosphites. [51][52][53] On the other hand, we are aware that this work only deals with monodentate tertiary phosphines and phosphites, therefore, further studies on bidentate and tridentate phosphorus compounds, as well as a wider selection are necessary.…”