S–H Bond cleavage versus thiol co-ordination in half-sandwich ruthenium complexes †

Pyridine- and pyrimidine-2-thiolate complexes of ruthenium

“…Their 1 H NMR spectra show a broad peak in the range of 9.50-9.51 ppm for the nitrogen bound proton. This implies that the heterocyclic thiol is bonded to the metal through the Satom of the thione form as observed for similar complexes [19,20].…”

“…The complexes [CpRu(PPh 3 ) 2 (SC 5 H 4 NH)]BPh 4 (5a) and [CpRu(PPh 3 ) 2 (SC 4 H 3 N 2 H)]BPh 4 (5b) are prepared following the method of Puerta [19,20] as shown in Scheme 3. The IR spectra of these orange stable complexes show the NH stretching band in the range of 3242-3256 cm À1 .…”

“…Several complexes of ruthenium with pyridine-2-thiolate complexes have been known in the literature [13][14][15][16][17][18][19][20][21]. In most of these complexes, the thiolato ligand is bonded to the ruthenium in an N,S-chelating (j 2 ) mode.…”

“…Cyclopentadienyl ruthenium complexes containing these thiolate ligands are rare. The complexes [CpRu(PP)(j 1 S-SC 5 H 4 -NH)]BPh 4 (PP = 2PEt 3 [19], dippe [20], dppf [21]) are prepared by reacting the corresponding Ru-chlorides with the HSpy in the presence of BPh À 4 . We are interested in the synthesis and reactions of ruthenium thiolate complexes [22][23][24].…”

Structure and Reactivity of Coordinatively Unsaturated Half‐Sandwich Iron, Ruthenium and Osmium Complexes

“…Interestingly, the addition of thiophenol yields the thiol adduct [Cp*Ru(HSPh)(dippe)] ϩ rather than the oxidative addition product. [92] One of our research group contributions has been the isolation and characterization of the metastable Ru IV alkynyl and hydroxyalkynyl hydrido complexes [Cp*-RuH(CϵCR)(P) 2 ] ϩ [(P) 2 ϭ dippe, PEt 3 , PMeiPr 2 ] [8,93Ϫ97] as intermediates in the alkyne to vinylidene tautomerization process. This process takes place both in solution and in the solid state.…”