Übergangsmetallkomplexe mit Schwefelliganden, LVIII / Transition Metal Complexes with Sulfur Ligands, LVIII

Abstract

The monocation [Ru(′S6′–CH=CH2)]+, [2]+, (′S6′–CH=CH2- = 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiaoctadec-17-ene(1–)) forms under normal conditions by S–C bond cleavage in an irreversible and selective reaction on treating salts of the dication [Ru(bzo2-18S6)]2+, [1]2+, (bzo2-18S6 = 2.3.11.12-dibenzo-1.4.7.10.13.16-hexathiacyclooctadecane) with one equivalent of base. This reaction demonstrates the drastic S–C activation in coordinated thioethers and should be taken into consideration when cofactors are isolated from metal sulfur enzymes.

Base-Induced Fragmentation of a Macrocyclic Thioether at an (Arene)ruthenium(II) Center. Generation of η1(S)-Ethenethiolate and η2(C,S)-Thioacetaldehyde

“…The first sequence is analogous to the deprotonation of [M(9S3) 2 ] 3+ (M = Co, Rh, Ir), which is induced by weak bases such as Et 3 N or water at pH > 4 and is reversed by acid (eq 5) . A similar process occurs on treatment of the six-coordinate ruthenium(II) dication of dibenzo-18S6 (eq 6) with NaOMe, although this process is irreversible …”

Reactions of Benzyne−Nickel(0) Complexes with Thioalkynes: Preparation and Coordination of Polydentate Thioethers Containing a 2,3-Naphthylene Backbone

“…Such a fragmentation is observed in the mass spectrum of the compound, and it has been reported to occur with several related ruthenium complexes. 40,41 In our case, it is not known whether this cleavage is catalyzed by the presence of nickel salts.…”

On the Relevance of Mono- and Dinuclear Iron Carbonyl Complexes to the Fixation and Stepwise Hydrogenation of N2

“…Note that the FeϪN bond length becomes shorter by 0.007 Å , which is paralleled by the lengthening of the NϪN bond by 0.008 Å . The CDA and NBO data in Table 5 show that the σ-donor properties of N 2 embraced by two iron tetracarbonyl fragments is hardly changed compared to 5a -only the π- [32] The small deviations of less than 0.052 Å are noteworthy as such Fe II (ЈS 4 Ј) complexes involving multidentate organosulfur ligands are often used as model compounds for the Fe-Mo, FeϪV and FeϪFe nitrogenases. [4,6,32] We note a non-negligible shortening of the FeϪN bond by 0.011 Å and a lengthening of the NϪN bond by 0.016 Å on going from 6a to its dinuclear pendant 10.…”