Formation of an Anionic Titanium(IV) Sulfido Dimer, {Na₂[CpTi(μ-S)(S)]₂·4THF}₂, by Elimination of CpH and H₂from Cp₂Ti(SH)₂upon Deprotonation with NaH

Abstract

A deprotonation reaction of Cp2Ti(SH)2 with NaH in THF yields {Na2[CpTi(μ-S)(S)]2·4THF}2, generated by unexpected elimination of CpH. This anionic dimer is unique in that it is the first organometallic titanium species containing terminal sulfido ligands. The latter are stabilized by interactions with THF-solvated sodium cations, thus imposing a syn TiS configuration.

An Anionic Dimer of Cyclopentadienyl- Titanium (IV) Sulfide: A Potential Precursor for Heterometallic Assemblies

“…A 1 H NMR spectrum of the resulting solution exhibits the formation of H 2 (δ 4.58 ppm) (Similar peak at δ 4.54 ppm, was reported by Ref. [16]. After some time a resonance around δ 6.00 ppm was observed, this can be attributed to an unknown decomposition product.…”

“…The 1 H NMR pattern is similar to that of the sodium compound Na 2 [CpTi(µ-S)(S)] 2 •4THF reported by Ref. [16] although the coordination environment of sulfur at the central titanium is different. The latter exhibits two Ti=S bonds, while compound 2 has only bridging Ti-S-Li units.…”

“…Moreover, hydrosulfide complexes that are considered as inorganic equivalents of thiols, can be potential building blocks for the synthesis of sulfur-bridged complexes [12][13][14][15] Indeed, most of the hydrosulfide complexes of group 4 transition metals such as [Cp 2 M(SH) 2 ] (Cp) η 5 -C 5 H 5 M = Ti, Zr) react with late transition metal complexes to afford hydrosulfide-or sulfide-bridged complexes. They have described [16] the dimeric species [CpTi-(µ-S)(S)] 2 2− while Ref. [17] reported comound (PhC(NSiMe 3 ) 2 ) 2 Ti(S) py.…”

Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium–sulfur bond

“… 36 Analogous to other known examples in transition metal chemistry, these uranium hydrosulfido complexes are suitable precursor molecules for the high-yield synthesis of terminal chalcogenido complexes, since the proton can be conveniently removed. 37 , 38 Additionally, the U–EH species can be seen as “proton-capped” terminal chalcogenido complexes and spectroscopic comparison to the analogous, truly terminal species provides unique insight into the nature of the chemical bond between uranium and the soft chalcogenido ligand. 27 – 29 , 32 Until today, there is only one structurally characterized uranium hydrosulfido complex reported in the literature, namely [(( Ad,Me ArO) 3 N)U–SH(DME)] (with ( Ad,Me ArO) 3 N 3– = trianion of tris(2-hydroxy-3-(1-adamantyl)-5-methylbenzyl)amine).…”

“…Due to their potential application as catalysts, transition metal hydrochalcogenido complexes (E = O, S, Se, and Te) have received considerable interest in recent years. 37 – 45 Most recently a uranium( iv ) hydroxo complex, namely [(( Ad,Me ArO) 3 mes)-U–OH], was found to be the key intermediate in the electrocatalytic production of dihydrogen from water. 9 …”