Thiocarbonyl complexes tungsten

Table 7.3 lists only few experimental data that can be used to estimate the accuracy of the theoretical results. The CCSD(T)/II values agree quite well with experiment (note, however, rather large error bars for the measured BDEs of the thiocarbonyl complexes). The MP2/II values are always larger than their CCSD(T)/n counterparts. The latter values show that the tungsten complexes always have the strongest M-Lbond while, in most cases, the molybdenum species have the lowest BDEs. 

B. D. Dombeck, and R. J. Angelici, Electrophilic and Oxidative Addition Reactions of Tungsten Thiocarbonyl Complexes, Inorg. Chem. 15, 2397-2402 (1976). 

The formation of tungsten complexes of thiiranes from diarylthioketones and W(CO)5-benzylidene complex is believed to occur via a thiocarbonyl ylide-like intermediate (115). 

Electrophilic addition to the sulfur atom of terminal thiocarbonyl ligands is a well-established route to thiocarbyne complexes of Group VI metals [2, 18, 19]. A requirement for the success of this approach is that the thiocarbonyl ligand be bound to a very electron-rich metal centre, preferably in an anionic complex. A methyltellurocarbyne complex of tungsten, [L(CO)2W=CTeMe]... 

---