Cyclopentadienyl tungsten complexes with thiocarboxylate and thiosulfonate ligands: Structures of CpW(CO)3SCOPh and CpW(CO)3SSO2-4-C6H4Cl

Pyridine‐Stabilized Cationic Silanethione Tungsten Complexes: Synthesis, Structures, and Reactivity

“…Crystal structure analysis using X‐ray diffraction revealed that complex 6 bears a four‐legged piano stool‐like structure with Cp*, three CO ligands, and an SSiR 2 N(Ph)C(PMe 3 ) 2 fragment (Figure 3). The W−S ( 6 a ; 2.5512(17) Å, 6 b ; 2.5758(9) Å) and S−Si ( 6 a ; 2.111(2) Å, 6 b ; 2.1072(12) Å) bond lengths are comparable to those observed for complex 4 (W−S; 2.5587(11) Å ( 4 a ), 2.545(2) Å ( 4 b ), S−Si; 2.1165(16) Å ( 4 a ), 2.111(2) Å ( 4 b )) [25] and structurally resemble Cp’(OC) 3 W(SR) complexes (Cp’=Cp* and Cp (η 5 ‐C 5 H 5 ), 2.49‐2.52 Å), [30b–d,36] and M−S−Si complexes (M=W and Mo, 2.11–2.14 Å), [25,30e,37] respectively. The bond lengths of the P−CN bonds ( 6 a ; P1−C12, 1.727(6) Å, P2−C12, 1.725(6) Å, 6 b ; P1−C22, 1.732(3) Å, P2−C22, 1.739(4) Å) are shorter than the P−C single bond lengths observed in complex 6 (P−C (Me) bonds, 1.78–1.81 Å), and comparable to the P−C unsaturated bond lengths reported for the [RPC(PPh 3 )−PPh 3 ] + compounds (1.71–1.76 Å) [38]…”