Pentamethylcyclopentadienyl Ruthenium(III) vs Hexamethylbenzene Ruthenium(II) in Sulfur-Centered Reactivity of Their Thioether-Thiolate and Allied Complexes

Abstract

The reactivity features of [Cp*Ru(III){eta(3)-tpdt)}] (7) and [(HMB)Ru(II)(eta(3)-tpdt)] (10) {Cp* = eta(5)-C(5)Me(5); HMB = eta(6)-C(6)Me(6); tpdt = 3-thiapentane-1,5-dithiolate, S(CH(2)CH(2)S(-))(2)} are presented, together with selected aspects of their (eta(3)-apdt) analogues 8 and 11 {apdt = 3-azapentane-1,5-dithiolate, HN(CH(2)CH(2)S(-))(2)}. This account will highlight the differences observed in their reactions with metal fragments of compounds of Ru and groups 10 and 11 in various coordination environments and with alkylating agents, including alpha,omega-dibromoalkanes. The mechanistic pathway of the alkylation of 7 will be discussed in some detail.

Kinetics and mechanisms in flow systems: reduction of SO2 on carbons

“…One important feature of thiolate complexes is their ability to undergo S-alkylation by the S N 2 mechanism. [95] This reactivity is also found in episulfides that behave as nucleophilic agents. [94] There are no reports on the reactivity of sulfinyl esters as S N 2 nucleophiles, but the bridge-O could act as a nucleophile.…”

“…The sulfur of the dioxathiolane intermediate may act as an effective nucleophile for the displacement of the halide of an alkyl halide. One important feature of thiolate complexes is their ability to undergo S‐alkylation by the S N 2 mechanism . This reactivity is also found in episulfides that behave as nucleophilic agents .…”

“…[85,86] It is also known that basic hydrolysis of sultines can easily occur with nucleophilic attack on the sulfinyl sulfur that would form a sodium salt. [87][88][89][90][91][92][93] The nucleophilic attack of hydroxide ion on the carbon atom of the episulfide ring would form a sulfide anion with Na + as the counterion in the first step, [94,95] eliminating S 2in the consecutive step. Alternatively, after reaction with a water molecule, a bisulfide anion could be released instead.…”

Synthesis and characterization of heterometallic Rh/Ru complexes supported by 1,2-dichalcogenolato-o-carborane ligands

“…Furthermore, multimetallic compounds have found medical applications [11]. Formation of these compounds by the use of bridging ligands [12][13][14] has played a decisive role in the systematic investigation of such systems. Among the bridging ligands commonly utilized, o-carborane dithiolato ligands have recently began to show the inimitable merits, especially stabilizing the organometallic complexes [2,15,16].…”

A Cyclometallated (Azobenzene)palladium(II) Complex of 1,4,7‐Trithiacyclononane: Synthesis and Reactivity with Thioether‐Dithiolate Metalloligands, Single‐Crystal X‐ray Diffraction Analyses and Electrochemical Studies

“…In recent years, we have reported the high efficacy of the Ru II and Ru III metalloligands [(HMB)Ru II (η 3 ‐tpdt)] ( 3 )8 and [(Cp*)Ru III (η 3 ‐tpdt)] ( 4 )9 [HMB = η 6 ‐C 6 Me 6 , Cp* = η 5 ‐C 5 Me 5 ; tpdt = S(CH 2 CH 2 S – ) 2 ] in the cleavage of metal–X bonds (X = chloride, phosphane, solvent ligand) in a variety of complexes, leading to di‐ and trinuclear homo‐ and heterometallic derivatives 10. This paper describes the comparative reactivity of species 3 and 4 with a target cyclometallated (azobenzene)Pd II (9S3) complex, the electrochemistry and crystal structure of which are also presented.…”