Synthesis, characterization and reactivity of oxothiomolybdates and their reactions toward sulfur dioxide.
Kim, Chang Gyoun
1993
Abstract
The facile addition reaction of sulfur dioxide, SO$\sb2,$ into the Mo(O)(S) group, depending on reaction conditions, afforded a multitude of products which contain the thiosulfite, thiosulfate, sulfite and sulfate dianions as bidentate chelating ligands terminally bound to the Mo atom. The reaction of ($\rm Et\sb4N)\lbrack (CP)Mo(O)(\mu$-$\rm S)\sb2Mo(O)(S)$) with SO$\sb2$ monitored by $\sp1$H NMR spectroscopy (Cp$\sp-$ protons) in a SO$\sb2$ saturated, $\rm CH\sb3CN$-d$\sb3$ solution in a sealed NMR tube over a period of time produces various complexes as products. The $\sp1$H NMR spectra and structures of these ((Cp)Mo(O)($\mu$-S)$\sb2$Mo(O)(L)) $\sp-$ complexes where L = SO$\sb3\sp{2-}$, S$\sb2$O$\sb3\sp{2-}$ and SO$\sb4\sp{2-}$ are described in detail. The reaction of SO$\sb2$ with the ($\rm Mo\sb2O\sb2S\sb2(S\sb{n})(S\sb{n\sp\prime})\rbrack \sp{2-}$ complexes (n = 2,4 and n$\sp\prime$ = 1,2) produces the ($\rm Mo\sb2O\sb2S\sb2(S\sb2O\sb3)\sb2\rbrack \sp{2-}$ complex through the ($\rm Mo\sb2O\sb2S\sb2(S\sb2O\sb3)(S\sb4)\rbrack \sp{2-}$ and ($\rm Mo\sb2O\sb2S\sb2(S\sb2O\sb3)(S\sb2O\sb2)\rbrack \sp{2-}$ intermediate complexes. The reaction of the ($\rm Mo\sb2O\sb2S\sb2(S\sb4)(S)\rbrack \sp{2-}$ and ($\{\rm Mo\sb2O\sb2S\sb2(S\sb4)(S)\}\sb2\rbrack \sp{4-}$ complexes with excess NaHSO$\sb3$ in a dimethyl formamide/water mixture yields ($\rm Mo\sb2O\sb2S\sb2(S\sb2)(S\sb2O\sb3)\rbrack \sp{2-}$. The S,O mixed bridged ($\rm Mo\sb2O\sb2(\mu$-S)($\mu$-O)(S$\rm \sb2O\sb3)(S\sb2O\sb3)\rbrack \sp{2-}$ complex is synthesized from the reaction of SO$\sb2$ with ($\rm MoO\sb2S\sb2\rbrack \sp{2-}$ and characterized. Ligand substitution reactions for this complex are discussed. The thermal reaction of SO$\sb2$ with the (Et$\sb4$N)$\sp+$ salts of ($\rm Mo\sb2O\sb2S\sb2(S\sb{n}(S\sb{n\sp\prime})rlbrack \sp{2-}$ complexes (n = 2,4 and n$\sp\prime$ = 1,2) in dimethyl formamide yields the tetrameric ($\{(\rm SO\sb4)Mo(O)(\mu$-S)$\rm sb2Mo(O)(SO\sb4)\}\sb2(\mu\sb4$-SO$\sb4)\rbrack\sp{6-}$ complexes. These complexes contain a unique $\mu\sb4$-SO$\sb4\sp{2-}$ ligand which is unprecedented in coordination chemistry of the SO$\sb4\sp{2-}$ ligand. The structures, spectroscopic properties and ligand substitution reactions of these complexes are described in detail. The synthesis and characterization of the mononuclear Mo complexes ($\rm Mo\sp{VI}(O)(S\sb2)\sb2(C\sb6H\sb5COS)\rbrack \sp-$, $\rm\lbrack Mo\sp{V}(O)Cl\sb5\rbrack\sp{2-}$, $\rm\lbrack Mo\sp{VI}(O)\sb2(Cl\sb2)(C\sb6Cl\sb4O\sb2)\rbrack \sp{2-}, \lbrack Mo(O)(S\sb2C\sb2(CN)\sb2)\sb2\rbrack \sp{2-}$ and ($\rm Mo\sp{VI}(O)\sb2(C\sb6Cl\sb4O\sb2)\sb2\rbrack \sp{2-}$ are described in detail.Other Identifiers
(UMI)AAI9409728
Subjects
Chemistry, General Chemistry, Inorganic
Types
Thesis
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