Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

Abstract

The quadruply bridged bimetallic dithiolato complex [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] (3) and the open-cage triple-decker complex [(Cp*W) 2 (μ-S)(μ-η 4 :η 4 -B 2 H 2 S 2 )] (2) have been prepared by treatment of CS 2 with in situ generated [(Cp*W) 2 (B 2 H 6 ) 2 ] (1) obtained by the reaction of [Cp*WCl 4 ] with [LiBH 4 ·thf ]. The solid-state X-ray diffraction structures of these complexes show the presence of doubly bridging η 2 -S 2 B 2 H 2 and η 2 -S 2 CH 2 ligands with a short W-W bond. While many dimolybdenumsulfur compounds are known, examples of the tungstendithilato complexes are relatively few, and in this respect, the isolation of [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] represents a rare exam- [a] 5434 ple of this type. Electronic-structure analysis, on the grounds of density functional theory (DFT), together with X-ray diffraction studies, has rationalized the presence of short W-W and B-B bonds. Large HOMO-LUMO gaps have been observed for both compounds, which is consistent with their thermodynamic stability. All of the compounds have been characterized by mass spectrometry, IR spectroscopy, and 1 H NMR, 11 B NMR, and 13 C NMR spectroscopy in solution, and the structural architectures have been unambiguously established by X-ray diffraction crystallographic analysis. Scheme 1. Structurally characterized dithiolato-bridged binuclear transitionmetal complexes [Mo = CpMo (I-V) and V = CpV (VI)]. [11a,13] Scheme 2. Synthesis of compounds 2, 2a, and 3.

Syntheses and structures of chalcogen-bridged binuclear group 5 and 6 metal complexes

“…49 However, it is found to be longer than those observed in [Cp*WCl 2 (l-H)] 2 50 and dithiolato-bridged complex of tungsten, [(Cp*W) 2 (l-S) 2 (l-g 2 -S 2 CH 2 )]. 51 The short W-W bond distance indicates a double bond interaction similar to Mo-Mo double bond (2.653(2) Å ) identified in [(CpMo) 2 (l-Se) 2 (l-SePh) 2 ]. 46 The short W-W distance is compatible with sharp acute W-S-W bite angles in the range of 61.79-64.53°.…”

Hetero-trimetallic complexes comprising bridging boryl and borylene ligands: an experimental and theoretical study

“…The M–M and M–S bond distances in 5 and 6 are comparable with that of corresponding metal thiolate complexes. 29,30 Based on the electron counting rules, 21,24 a trimetallic chain having two M–M′ bonds is expected to possess 50 valence electrons. The total number of VE available in 5 and 6 are indeed 50.…”

Synthesis of Trithia-Borinane Complexes Stabilized in Diruthenium Core: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BR}] (R = H or SMe)

“…The chemistry of transition-metal complexes with main group elements, particularly with chalcogen ligands, are of substantial importance. The homo-and heterometallic sulfido complexes with a wide range of substrates are well-documented in the literature [50][51][52][53]. In contrast, thioborates are not regularly seen in the coordination sphere of transition metals, mostly due to the lack of synthetic routes.…”