[(μ₂-H)Ru₃(CO)₉{μ₃-NS(O)MePh}]:  An Electron-Deficient Trinuclear Cluster Containing a Chiral Sulfoximido Cap

Abstract

The chiral sulfoximine MePhS(O)NH reacts with [Ru3(CO)12] to give, with N−H activation and coordination of the H and NS(O)MePh fragments to the trinuclear ruthenium framework, the 46 electron cluster [(μ2-H)Ru3(CO)9{μ3-NS(O)MePh}] (1) which, in accordance with its electron-deficiency, takes up carbon monoxide reversibly to give the electron-precise 48 electron cluster [(μ2-H)Ru3(CO)10{μ2-NS(O)MePh}] (2).

Synthesis and Crystal Structure of a Unique and Homochiral N,S-Bonded N,N‘-Bis(tert-butanesulfinyl)amidinate Rhodium(I) Complex

“…Chiral ligands containing both nitrogen and sulfur have recently received considerable attention in asymmetric catalysis thioamides, and thioureas . All existing chiral variants of these ligands depend on the chirality about the appended α-carbon centers.…”

“…All existing chiral variants of these ligands depend on the chirality about the appended α-carbon centers. A few examples of chirality on sulfur have been reported for alternative ligand scaffolds as exemplified by the neutral sulfoximido cap structure reported by Bolm and Süss-Fink and the β-amino sulfoxide ligand reported by Pettinari and co-workers …”

Sulfoximines: Structures, Properties and Synthetic Applications

“…The very interesting electron deficient trinuclear ruthenium cluster 495 (refcode: TAVPOV, Scheme 122) 10 is an exciting entry to the discussion of the synthesis and applications of N,S-donor substituted sulfoximine ligands (Scheme 117, Type B). 10,268…”

Electron counting and bonding analysis in triruthenium clusters containing sulfoximido ligands: true or false electron-deficient systems?

“…The sulfur-nitrogen bond in 1 (1.566 A , ) [2] can be interpreted as an N S double bond in comparison with methionylsulfoximine (1.529 A , ) [4], which would leave 3e − on the nitrogen atom of the N S(O)MePh fragment, in accordance with an electron count of 46e − for the cluster. In addition, apart from the slightly longer Ru Ru bond carrying the m 2 -hydrido bridge (2.831 A , ), the Ru Ru bonds in 1 are distinctly shorter (2.674 and 2.683 A , ) [2] than the average ruthenium -ruthenium distance in Ru 3 (CO) 12 (2.854 A , ) [5], which we interpreted in terms of two missing electrons in 1 with respect to the 18e − rule (48e − for the Ru 3 system). The most striking argument for the electron deficiency of 1 came from its reactivity: 1 was found to absorb carbon monoxide to give the addition product Ru 3 (CO) 10 …”

“…The only high-yield product of this reaction, Ru 3 (CO) 9 (m 2 -H)[m 3 -NS(O)MePh] (1, Eq. (1)), which we isolated in both enantiomeric forms and characterized by single-crystal X-ray crystallography, was considered to be an electron-deficient 46e − cluster (taking into account the sulfoximido cap as a 3e − ligand [2]. …”