14971-44-9Relevant academic research and scientific papers
SOLID-STATE STRUCTURE AND REACTIVITY IN SOLUTION V. RING-CLOSURE IN THE (η1-2,2,8,8-TETRAMETHYL-3,7-DITHIANONANE)TETRACARBONYLTUNGSTEN(0) INTERMEDIATE
Dobson, Gerard R.,Dobson, Charles B.,Halverson, D. Eric,Mansour, Saber E.
, p. C27 - C32 (2007/10/02)
Pulsed laser flash photolysis of (η2-DTN)W(CO)4 (I, DTN = 2,2,8,8-tetramethyl-3,7-dithianonane) in 1,2-dichloroethane induces ring-opening to afford the solvated 1-DTN)W(CO)4> intermediate II.Rates of unimolecular ring-closure for this intermediate to afford I and of bimolecular combination of I with triisopropyl phosphite (L) have been determined, as have activation parameters for the ring-closure pathway.The relatively high enthalpy of activation (12.0(6)kcal/mol) suggests distortion in I induced upon chelate ring-closure.Rates of interaction of L at an open coordination site (one produced via CO loss from an octahedral (chelate)M(CO)4 complex) are some two orders of magnitude faster than are those for a shielded site produced through ring-opening, suggestive of extensive steric interaction between the bidentate ligand and L for the combination process in the latter.
