A dimolybdosulfenamide: condensations and crystal structures. Sulfur invertomer structural effects

Activation of Ligand Reactivity: Thiolate C−S and Dithiophosphate Ester C−O Heterolyses within a Dimolybdenum(V) System

“…The solution NMR spectra showed isomers corresponding to inversion of the pyramidal thiolate−sulfur bridges. As previously documented for RS{Mo 2 }S 2 and related derivatives, − , these are freely fluxional invertomers; they are labeled distal ( d ) or proximal ( p ) depending on the thiolate orientation with respect to the tolylimido rings. For MeS{Mo 2 }SMe + , the dominant solution isomer contains both thiolate groups in distal orientation (distal−distal, d - d ); this isomer is portrayed in the prior structural illustrations for 3 .…”

“…The invertomer distributions are nonstatistical with a clear distal preference. Structural and electronic differences between distal and proximal invertomers have been previously discussed for several ZS{Mo 2 }S compounds …”

“…For EtBr, no reaction was observed through 2 h. The summary trend was therefore MeBr > BzBr > EtBr. The relative celerity of MeBr was a steric result arising from the nearby acetate bridge and also the tolylimido rings when the thiolate group is in the inverted position (as described in Part 2) . The classical electronic activation of a benzylic substrate was secondary in this case to steric factors when compared to MeBr, although the electronic aspects did govern the relative outcomes of BzBr and EtBr.…”

“…Each structure was refined by full-matrix, least-squares methods minimizing ∑ w (| F o | − | F c |) 2 , where w = [σ 2 ( F )] -1 . Each structure contained some disorder within the dithiophosphate ethoxy groups, which has been common within related dimolybdenum complexes. ,, Although this was unfortunate in this work due to the interest in the dithiophosphate ligands themselves, the disorders limited but did not eliminate useful results to the extent discussed herein.…”

Isomerization, reactivity, and structural study of a thioperoxide-bridged dimolybdenum(V) dimer.

“…Only a few metal-sulfur systems have well characterized reactions at a sulfide, disulfide, or polysulfide site. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] In the course of our studies, we recently focused our interest on the chemistry of a particularly stable molybdenum-sulfur complex, the methyl ..…”