in tetrahydrofuran reductive disproportionation; mechanism discussed;; IR;;

in tetrahydrofuran reductive disproportionation; mechanism discussed;; IR;;

carbon oxide sulfide in tetrahydrofuran byproducts: Na2(CO3), Na2(CS3)*H2O; under Ar or N2; adding dry COS to rapidly stirred soln. of Na2(W(CO)5) (-78°C, 30 s), stirring (5 min), settling (25 min); filtering (-78°C), washing (H2O, room temp.), washing (Et2O, -60°C), drying (slow stream of air);

oxalyl dichloride in tetrahydrofuran byproducts: naphthalene, COS, CO; under Ar or N2; injecting PhNCS into stirred THF soln. of Na2(W(CO)5) (-78°C), injecting oxalyl chloride into stirred soln., stirring (5 min), warming to room temp.; removing solvent (reduced pressure), extg. (n-pentane), filtering, evapg. solvent (reduced pressure), subliming naphthalene and W(CO)6 (0.02 Torr, 40°C, 1 h), extg. residue (n-pentane), filtering, removing solvent (reduced pressure);

in tetrahydrofuran byproducts: Na[OTs]; a THF soln. of PhCHDCHDOTs was added dropwise at -78°C under inert atmosphere to a freshly prepd. soln. of W-complex in THF (IR monitoring), after the soln. was warmed to -20°C, PPN(OTs) was added, mixt. was stirred for 1 h at room temp.; reaction mixt. was centrifuged, filtered through Celite, evapd. in vacuo, residue repptd. several times with hexane from THF, washed with etherand hexane, dried in vacuo; a small quantity of μ-HD complex was notsepd. from the main product;

in tetrahydrofuran under Ar or N2; injecting PhNCO into stirred soln. of Na2(W(CO)5) in THF (-78°C, 5 min), warming to room temp., adding second portion of PhNCO; detected by IR; not isolated;