Synthesis and X-ray Structure of an H₂S Complex, RuCl₂(P-N)(P(p-tolyl)₃)(SH₂) (P-N = o-(Diphenylphosphino)-N,N-dimethylaniline)

Abstract

The five-coordinate complexes RuCl2(P-N)(PR3) (P-N = o-(diphenylphosphino)-N,N-dimethylaniline; R = Ph or p-tolyl) in solution reversibly bind H2S at ambient conditions. The isolated products are characterized spectroscopically, and the p-tolyl species is structurally characterized by X-ray analysis; there is close to octahedral geometry at the Ru with cis-chlorides and the H2S trans to a chloride. The p-tolyl species is also formed in the solid state by reaction of H2S with the powdered five-coordinate precursor.

Synthesis, characterization, reactivity and theoretical studies of ruthenium carbonyl complexes containing ortho-substituted triphenyl phosphanes

“…The (np) ligand coordinates strongly through both nitrogen and phosphorus, resulting in a highly stable structure. The tendency to produce strongly chelated complexes is typical of this particular (np) ligand [33,34] and examples of non-chelated metal complexes of this ligand are, to the best of our knowledge, not reported. In contrast, other (np) ligands such as the 2-(diphenylphosphino)-pyridine (PPh 2 py) [35][36][37] and the 2-(diphenylphosphino)-1-methyl-imidazole (dpim) [38] show slightly better hemilabile properties and the non-chelated metal complexes containing these phosphanes have been identified.…”

31P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere

“…One of our groups first reported in 1993 on the square-pyramidal complexes trans -RuCl 2 (P-N)­(PR 3 ) (R = Ph, p -tolyl; P-N = o -diphenyl­phosphino- N , N ′-dimethyl­aniline) and their ability to bind H 2 and N 2 to form, as final products, the six-coordinate cis -RuCl 2 (P-N)­(PR 3 )­L (L = H 2 , N 2 ) complexes . Subsequently, the other relatively small molecules H 2 S, , N 2 O, thiols, CO, NH 3 , and HCCPh, which is converted to coordinated CCHPh, reacted similarly to form related six-coordinate complexes, in which the chloride ligands are either cis or trans . Scheme shows the cis and trans products for these systems, although the L = H 2 O and alcohol species were made via reactions with RuCl 2 (P-N)­(PR 3 ) that was formed in situ from RuCl 3 (PR 3 ) 3 complexes; the most recent report describes a corresponding cationic cis -NO + species that was formed by reaction of fac- RuCl 3 (NO)­(P-N) with PPh 3 .…”

Transdermal hydrogen sulfide delivery enabled by open metal site metal-organic frameworks

“…This short distance is consistent with reported magnesium complexes containing thiol or thiolate ligands, which have S⋅⋅⋅Mg bond distances of 2.3-2.4 Å (SI Table S5). [75][76][77][78][79] The few reported complexes in which either H2S or SH − is directly bound to a metal center, including Mn, 80 Os, 81 and Ru [82][83][84][85] complexes, also possess comparable metal-sulfur bond distances of 2.33-2.45 Å (SI Table S6). The interaction between H2S and the Mg 2+ site in Mg2(dobdc) is on the shorter side of this range likely due to the small size of the Mg 2+ cation.…”