Photolysis of a methanol solution containing substituted alkyne, group VI metal hexacarbonyl and P₄S₁₀ at low temperature under an inert atmosphere leads to metal-sulfur coordinated complexes of chromium, molybdenum, and tungsten. The structure of pentacarbonylthioacetylferrocene-S-chromium (1) is confirmed by single crystal x-ray diffraction study and both the complexes (1 and 2) are confirmed using IR and NMR spectral studies. The sulfur-coordinated metal carbonyl complexes are thought to be formed by the initial activation of metal carbonyl with acetylenic ligand which then rearranges into metal coordinated thioacetylferrocene by dithiophosphoryl radical (formed in situ by reaction of P₄S₁₀ and methyl alcohol under photolytic condition). The stability of pentacarbonylthioacetylferrocene of group VI metal complexes are further compared with their acetylferrocene derivatives of Group VI metal complexes using DFT studies. Density functional theory was performed on six complexes [(CO)₅ME=CFcCH₃] (where M = Cr, Mo and W; while E = O and S) to assess their geometry and electronic structure aspects. Natural bonding orbital (NBO) and energy-decomposition analysis (EDA) were carried out to probe the nature and strength of the M-E interactions. NBO and EDA analysis predict M-E bond strength in the following order: Cr-E < Mo-E < W-E. The M-E bond covalency increases as we move down the group from Cr, Mo to W, which rationalizes the observed trends in the M-E bonds. While comparing the nature of the E (O and S) linkage in bonding, we found that -S analogue shows exceptionally robust σ and π interactions compared to the -O analogue. The reasonably strong M-S interactions resulted in the isolation of these -thio analogues.

在惰性气氛下低温光解含有取代炔、VI 族六羰基金属和 P ₄ S ₁₀的甲醇溶液，产生铬、钼和钨的金属-硫配位配合物。五羰基硫代乙酰基二茂铁-S-铬 ( 1 ) 的结构由单晶 X 射线衍射研究证实，配合物 ( 1和2 ) 均使用 IR 和 NMR 光谱研究证实。硫配位的金属羰基配合物被认为是通过羰基金属与炔配体的初始活化形成的，然后通过二硫代磷酰基重排成金属配位的硫代乙酰二茂铁（通过 P ₄的反应原位形成）S ₁₀和甲醇在光解条件下）。使用 DFT 研究进一步比较了 VI 族金属配合物的五羰基硫代乙酰二茂铁的稳定性与其 VI 族金属配合物的乙酰二茂铁衍生物。密度泛函理论在六个配合物上进行 [(CO) ₅ ME=CFcCH ₃]（其中 M = Cr、Mo 和 W；而 E = O 和 S）来评估它们的几何形状和电子结构方面。进行了自然键合轨道（NBO）和能量分解分析（EDA）以探测ME相互作用的性质和强度。NBO 和 EDA 分析按以下顺序预测 ME 粘合强度：Cr-E < Mo-E < WE。当我们将组从 Cr、Mo 向下移动到 W 时，ME 键共价增加，这使观察到的 ME 键趋势合理化。在比较键合中 E（O 和 S）键的性质时，我们发现与 -O 类似物相比，-S 类似物显示出异常强大的 σ 和 π 相互作用。相当强的 MS 相互作用导致这些-硫代类似物的分离。