Gezielte Synthese von O‐ und S‐Sulfinato‐Komplexen einiger Übergangsmetalle, II. Das Verhalten von Bis(organosulfinato)‐metall‐Komplexen gegenüber zweizähnigen Donorliganden

Abstract

w Bei der Einwirkung von zweizahnigen Donorliganden auf die Bis(organosu1finato)-metall-Komplexe l a -l g werden, entspr. GI. (l), mit Ansnahme von 4, neuartige Doppel-(2a bzw. 2b) und Mono-0-Sulfinato-Komplexe (3a 3c) erhalten und charakterisiert. Die Additionsreaktionen sind abhangig von der TonengroRe der zweiwertigen Metalle und dem nucleophilen Charakter der RSO*--Liganden. Durch IR-spektroskopische Untersuchungen kann in allen Fallen entschieden werden, ob Soder 0-Sulfinato-Komplexe vorliegen.

Coordination Chemistry of the (η6-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, and Tetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and Catalytic Diastereoselective Nitroaldol Reaction Studies

“…Also the reaction of compound 3 with AgO 3 SCF 3 in methanol leads to [Ru(η 6 - p -cymene)(κ 3 -Tp)][O 3 SCF 3 ]·H 2 O ( 5 ). Further support of our structural hypothesis for 5 comes from the observation of the characteristic absorption in the 1000−1200 cm −1 region, typical of a noncoordinated [O 3 SCF 3 ] − , in accordance with the ionic formulation of 5 (Scheme ). Moreover, 3 reacts with NaN 3 in acetone, affording the compound [Ru(η 6 - p -cymene)(κ 2 -Tp)(N 3 )] ( 6 ) (Scheme ).…”

“…The value of 0.14 vs NHE was estimated before for Tp at the phosphine complex [Ru(Tp)Cl(PPh 3 ) 2 ]. The variation of the estimated E L parameter of Tp can possibly account for (i) a (slight) failure of the additive model of eq , (ii) the need to adjust the S M and I M values (proposed for the octahedral coordination) to the pseudo-octahedral half-sandwich π-arene-type coordination of the Tp complexes, (iii) the eventual dependence of the E L value (for Tp) on the coordination metal center, and/or (iv) the irreversibility of the oxidation (in the cases of 3 , 4 , and 5 ).…”

Enhancing Tris(pyrazolyl)borate‐Based Models of Cysteine/Cysteamine Dioxygenases through Steric Effects: Increased Reactivities, Full Product Characterization and Hints to Initial Superoxide Formation

“…The ATR‐IR spectra of the solid complexes 5 a , 5 b and 5’b show the characteristic bands of N−H, B−H and C=O vibrations shifted compared with the parent compounds. In addition absorptions in the fingerprint region between 990 and 950 cm −1 can be assigned to S=O stretching vibrations . Also bands for Fe−O vibrations could be identified between 650 and 480 cm −1 , which have reasonable intensity in case of complexes 5 b and 5’b , while those of 5 a are quite weak (Table , Figure S8).…”

Bond Isomerism in Sulfinato Complexes of Transition Metals

“…The occurrence of oscillation in the system under consideration can be explained in the following way: After the components have been added together reactions (l), (2), and (3) start successively, the bromide formed in reaction (3) having an inhibiting effect on reaction (1). A noticeable inhibition of reaction (1) could be achieved at time B in Fig.…”

“…The reaction between Fe(O,SR),(OH,), (I)''] and 2,2'-bipyridine (= bipy) shows a marked dependence on the solvent: In tetrahydrofuran the reactants give exclusively Fe(O,SR),bipy (Z) [3]; in pyridine Fe(O,SR),(bipy), (3) is obtained; and in water the ionic compound [ F e ( b i~y )~] (02SR), (4) is formed quantitatively.…”