Characterization of reversible reactions of isocyanides with molybdenum dithiolate complexes

Journal Article · Wed Jul 16 04:00:00 EDT 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00535a016· OSTI ID:6841137

Miller, D J; DuBois, M R

Dimeric molybdenum complexes with bridging dithiocarbonimidate ligands of the formula (C/sub 5/H/sub 5/MoS/sub 2/CNR)/sub 2/ (where R = CH/sub 3/, CH/sub 2/C/sub 6/H/sub 5/, C/sub 6/H/sub 11/, and n-C/sub 4/H/sub 9/) have been synthesized and characterized. The syntheses involve the room-temperature reactions of excess isocyanides with solutions of the dimeric complex (C/sub 5/H/sub 5/MoSC/sub 3/H/sub 6/S)/sub 2/. During the course of these reactions, propene is displaced from the sulfur atoms of the bridging dithiolate ligands. Addition of excess alkene reverses the above reactions. Equilibrium constants have been calculated for the following reactions by integration of NMR resonances: (CH/sub 3/C/sub 5/H/sub 4/MoSC/sub 2/H/sub 4/S)/sub 2/ + RNC reversible (CH/sub 3/C/sub 5/H/sub 4/Mo)/sub 2/(SC/sub 2/H/sub 4/S)(S/sub 2/CNR) + C == C, K/sub 1/ = 2.9 +- 0.2; (CH/sub 3/C/sub 5/H/sub 4/Mo)/sub 2/(SC/sub 2/H/sub 4/S)(S/sub 2/CNR) + RNC reversible (CH/sub 3/C/sub 5/H/sub 4/MoS/sub 2/CNR)/sub 2/ + C == C, K/sub 2/ = 0.7 +- 0.1 (R = CH/sub 2/C/sub 6/H/sub 5/). The dithiocarbonimidate complexes react cleanly with the electrophiles CH/sub 3/OSO/sub 2/F and HOSO/sub 2/CF/sub 3/ to form (C/sub 5/H/sub 5/MoS/sub 2/CNRR')/sub 2//sup 2 +/ where R' = H or CH/sub 3/. These products have been characterized by spectral and conductivity methods. The reactions of the dithiocarbonimidate complexes with reducing agents and with carbon monoxide are discussed. 1 figure, 2 tables.

• Research Organization: Univ. of Colorado, Boulder
• OSTI ID: 6841137
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 102:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CHEMICAL REACTIONS
COMPLEXES
DIMERS
ELEMENTS
HYDROCARBONS
MAGNETIC RESONANCE
MOLYBDENUM COMPLEXES
NONMETALS
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
PROPYLENE
RESONANCE
SULFUR
TRANSITION ELEMENT COMPLEXES