Pentacarbonyl(imidazolidine-2-thione-κS)tungsten(0)

Abstract

In the title complex, [W(C3H6N2S)(CO)5], the W atom displays an octa­hedral coordination with five CO mol­ecules and an imidazolidine-2-thione mol­ecule. The W(CO)5 unit is coordinated by the cyclic thione ligand through a W—S dative bond. The W—S and C—S bond lengths are 2.599 (2) and 1.711 (9) Å, respectively. This last distance is significantly longer than that of free cyclic thio­ureas. The geometry of the title compound suggests sp 3-hybridization of the S atom caused by the greatly polarized linkage W—S—C bond angle, which is close to tetra­hedral [109.50 (3)°]. In the crystal packing, N—H⋯O and N—H⋯S hydrogen-bonding inter­actions stabilize the structure and build up chains parallel to [101].

Experimental and four‐component relativistic DFT studies of tungsten carbonyl complexes

“…1.536 Å) is longer than the standard C sp3 –C sp3 bond length. The sulfur atom of the thiol group is sp 3 hybridized as is confirmed from the W–S–C6 bond angle of 109.5 o in the X‐ray structure and 100.5 o in the optimized geometry.…”

“…We note that for both 1 and 2 , the inclusion of solvent effects improves the agreement between the calculated and experimental values. For this reason, we believe that the solvent and relativistically corrected proton chemical shifts of 3 provide reliable estimates for the δ ( 1 H) for which no experimental observations have been reported …”

“…The latter compound contains two heavy metal atoms, tungsten and tin, making it an interesting candidate for relativistic NMR property calculations. The synthesis and experimental NMR parameters of the remaining two molecules, η 2 ‐norbornene‐pentacarbonyltungsten ( 2 ) and imidazolidine‐2‐thione‐pentacarbonyltungsten ( 3 ), have been reported previously by Górski et al , and Merniz et al ,, respectively. The structures of all molecules together with their atom numbering are shown in Fig.…”