Alkylation of a dimolybdenum SO bridge, subsequent reactions, and characterization of the thioperoxide bridge.
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.
Tuong
Chi Minh
CM
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
Hammons
Whitney K
WK
Howarth
Ashley L
AL
Lutz
Kelly E
KE
Maduvu
Ackim D
AD
Haysley
Laura B
LB
Allred
Brian R T
BR
Hoyt
Lenore K
LK
Mashuta
Mark S
MS
Noble
Mark E
ME
D000478:Alkylation; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D010545:Peroxides / Q000737:chemistry*; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*
D008024:Ligands; D009942:Organometallic Compounds; D010545:Peroxides; D013455:Sulfur; D008982:Molybdenum; D010100:Oxygen