Alkylation of a Dimolybdenum SO Bridge, Subsequent Reactions, and Characterization of the Thioperoxide Bridge

Abstract

The SO bridge of the complex, [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SO)], 1, displayed nucleophilicity at O, giving alkylation products [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-SBn)(mu-SOR)](+), 4(+), which contained the thioperoxide bridge. These cations were then subject to nucleophilic attack by two pathways. Debenzylation of the bridge thiolate in 4(+) afforded neutral [Mo(2)(NTo)(2)(S(2)P(OEt)(2))(2)(mu-O(2)CMe)(mu-S)(mu-SOR)], 5; de-esterification of a dithiophosphate ligand in 4(+) gave [Mo(2)(NTo)(2)(S(2)P(O)(OEt))(S(2)P(OEt)(2))(mu-O(2)CMe)(mu-SBn)(mu-SO)], 6, which contained a monoester, dithiophosphate ligand. Complex 1 gave a slow and clean reaction in the crystalline state, further demonstrating its nucleophilicity by attacking a neighboring molecule in its lattice. X-ray crystallography confirmed the thioperoxide linkage and revealed structural similarities of the Mo(2)(mu-SOR) unit to sulfenate esters (RSOR) and related derivatives.

Strong Be–Be bonds in double-aromatic bridged Be2(μ-SO) molecules

“…Therefore, it can act as a bi-radical ligand and tends to form compounds in which sulfur monoxide is bridged between two metal centers. 23–26 Furthermore, previous research showed that the Be–S bonds are sufficiently strong, and therefore, structures formed from this bond are thermodynamically stable. 21 So, in light of theoretical research on compounds with Be–Be bonds, the end-on sulfur-bound sulfur monoxide complex of Be 2 ( i.e.…”

Progress toward the Isolation of Late Metal Terminal Sulfides

“…We have also examined the reactivity of our novel cis ‐thiohyponitrite complex 40 . Remarkably, gentle thermolysis of 40 in C 6 H 6 results in extrusion of N 2 from the [SNNO] 2– ligand, and formation of [K(18‐crown‐6)][ t Bu LNi(η 2 ‐SO)] ( 47 ) (Scheme ), a rare example of a structurally characterized thioperoxide complex . Significantly, addition of excess CO to 47 results in O‐atom abstraction and re‐formation of the terminal sulfide 32 , along with CO 2 .…”