Progress toward the Isolation of Late Metal Terminal Sulfides

Abstract

This Minireview examines the synthesis and characterization of late metal (i.e., groups 8-12) terminal sulfides, along with a discussion of their electronic structures. We discuss both examples where a terminal sulfide was isolated, as well as those examples where a terminal sulfide was invoked as an unobserved intermediate. Additionally, where appropriate, we contextualize our discussion by comparisons to either early [a] M.

Terminal Imido Complexes of the Groups 9–11: Electronic Structure and Developments in the Last Decade

“…Section 6 addresses gas‐phase and matrix studies of groups 9–12 terminal nitrido complexes. Beyond the aged, yet still leading, reviews on the electronic structure of multiple bonded complexes, [3] we further would like to draw the attention of the dedicated reader to recent summaries on terminal sulfido‐ [4] and oxo‐ complexes of the late 3 d transition metals in the context of O−O bond formation and activation [5] . This is likewise the case for a perspective on functional group transfer with coordinatively unsaturated, charge‐separated multiple bonded transition metal complexes (“vicinal zwitterions”) [6]…”

Unequivocal Characterization of an Osmium Complex with a Terminal Sulfide Ligand and Its Transformation into Hydrosulfide and Methylsulfide

“…Some terminal sulfide derivatives of these elements have been proposed as transient species for the formation of condensed metal frameworks. , In two cases, the coordination of a terminal sulfur atom to a platinum group metal has been suggested, but they are controversial: the osmium salt mentioned above and a [Ru 2 Pd] cluster containing a Pd–S terminal bond . Although the latter has been characterized by X-ray diffraction analysis, the structural parameters obtained and therefore the validity of the structure seem to raise doubts . This Communication shows the stabilization and complete and unequivocal characterization of an osmium terminal sulfide complex, which represents a rare example within the chemistry of platinum group elements.…”

“…The salt was obtained in low yield from the reaction crude resulting from the treatment of [N­( n -Bu) 4 ]­[Os­(N)­(CH 2 SiMe 3 ) 2 Cl 2 ] with Li 2 S. The crude containing mainly binuclear species . Like terminal oxo compounds, terminal sulfide complexes are frequent for iron and the transition elements found on the left side of Group 8, while they are very rare for the 3d metals on the right side and practically unknown for the platinum group metals . Some terminal sulfide derivatives of these elements have been proposed as transient species for the formation of condensed metal frameworks. , In two cases, the coordination of a terminal sulfur atom to a platinum group metal has been suggested, but they are controversial: the osmium salt mentioned above and a [Ru 2 Pd] cluster containing a Pd–S terminal bond .…”