The Pivotal Role of Ru‐dmso Compounds in the Discovery of Well‐Behaved Precursors

Abstract

This paper is a tribute to the rich chemistry and great versatility of ruthenium-dmso precursors: over the years, from a handful of complexes we prepared literally hundreds of derivatives with all types of ligands, from mono-to polydentate, from pure σ-donors (e.g. NH 3 ) to phosphines and strong π-acceptors such as CO and NO. This systematic and extensive investigation had a thread of thought running through it: the identification of compounds that might have functional roles, either because they possess peculiar physical-chemical properties or [a]

Osmium(IV) Halide Complexes with Dimethyl Sulfoxide[H(dmso)2][OsX5(dmso‐κO)], X=Cl, Br: Synthesis, Structure, and Properties

“…The interest towards platinum metal complexes with DMSO is further stimulated by their prospective applications as precursors of compounds with tailored functional properties, such as homogeneous catalysts or biologically active substances …”

“…[1][2][3][4][5] The deliberate synthesis and isolation of bonding isomers and diastereomers as well as elucidation of factors favoring their formation made a notable contribution to the contemporary coordination chemistry. [2,3] The interest towards platinum metal complexes with DMSO is further stimulated by their prospective applications as precursors of compounds with tailored functional properties, [3,6,7] such as homogeneous catalysts [8][9][10][11][12] or biologically active substances. [13][14][15][16] Even among platinum metal complexes with DMSO, osmium compounds take a special place.…”

“…[25] Meanwhile, the mono-substituted anion [OsBr 5 (dmso)]predominates in mixed acetone-DMSO solutions (5 vol Based on the above experimental observations we elaborated a special procedure to enhance the yield of the desired products. It implies the preliminary conversion of the [OsX 6 ] 2dianion into the [OsX 5 (Me 2 CO)]monoanion (X = Cl, Br), in which a weakly coordinated acetone molecule can be readily substituted by a DMSO molecule according to the Scheme: 6 ] in acetone should be aged for several hours to promote the formation of the [OsX 5 (Me 2 CO)] À mono-substituted anions, which can be controlled by UV-vis spectroscopy. Addition of DMSO to these aged solutions followed by salting out with diethyl ether affords target complexes 1 and 2 as needle-shaped yellow and red crystals, respectively.…”

Ruthenium (II) complexes bearing thioether‐appended α‐iminopyridine ligands: Arene precursors permit access to κ2‐N,N and κ3‐N,N,S complexes

“…Attempts to isolate and fully characterize this product resulted in decomposition. Although the putative [ L1 ‐Ru(PPh 3 ) 2 Cl] BF 4 was precipitated from CDCl 3 solution by addition of copious Et 2 O, 1 H and 31 P spectral features of this isolated solid in DMSO‐ d 6 solution suggest several phosphorus‐containing species (δ = 50.33, 36.08, 17.40) are formed, likely as a result of solvation . Notably, this complex is different from the [ L1 ‐Ru(PPh 3 )Cl 2 ] observed when L1 is heated in the presence of Ru(PPh 3 ) 3 Cl 2 in benzene …”

Emissive Ruthenium–Bisdiimine Complexes with Chelated Thioether Donors

“…Synthesis, Purification, and Analysis: 2-(Mercaptomethyl)pyridine, [16] [RuCl 2 (dmso) 4 ], [17] [RuCl 2 (dmso) 2 (1)], [18] and tpa [5e] were prepared according to previously reported methods. All other chemicals were purchased from Sigma-Aldrich and used without further purification.…”