Synthesis of [(Me3SiNCH2CH2)(3)N](3-) and [(C6F5NCH2CH2)(3)N](3-) complexes of molybdenum and tungsten that contain CO, isocyanides, or ethylene

Paramagnetic complexes of the type [N3N]MoL ([N3N](3-) = [(Me3SiNCH2CH2)(3) N](3-); L = CO, RNC, C2H4) have been prepared by displacing dinitrogen from [N3N]Mo(N-2). [N3N]Mo(CO) was reduced by magnesium powder in the presence of Me3SiCl to yield the diamagnetic oxycarbyne complex [N3N]Mo=COSiMe3, whi le oxidation of [N3N]Mo(CN-t-Bu) with [Cp2Fe]OTf yielded {[N3N]Mo(CN-t-Bu)} OTf. Thermolysis of [N3N]Mo(CN-t-Bu) resulted in loss of a t-Bu radical to yield [N3N]Mo(CN), which was structurally characterized, [N3NFML ([N3NF](3- ) = [(C6F5NCH2CH2)(3)N](3-) M = Mo, W; L = CO, RNC) complexes have been pre pared by one-electron reduction of [N3NF]M(OTf) in the presence of L. An X- ray study of [N3NF]W(CN-t-Bu) showed it to contain a bend isocyanide ligand . Anionic CO complexes were prepared by the two-electron reduction of [N3NF ]M(OTf) in the presence of CO. An X-ray study of {[N3NF]W(CO)(2)}Na(ether)( 3) revealed it to have a pseudo-octahedral structure in which sodium is bou nd to the CO trans tb the amine donor atom. Treatment of {[N3NF]M(CO)}(-) c omplexes with Me3SiCl gave oxycarbyne complexes [N3NF]M=COSiMe3. Reaction o f [N3NF]WCO with V(Mes)(3)(THF) yielded [N3NF]W(CO)V(Mes)(3), the structure of which was determined in an X-ray study. Cationic [N3NF](3-) complexes c ould be prepared that contain up to 3 equiv of isocyanide. An X-ray study o f {[N3NF]W(CN-t-Bu)(3)}BPh4 showed it to be a seven-coordinate species with one isocyanide located in the equatorial plane and the other two isocyanid e ligands in the apical pocket. Reduction of [N3NF]W(OTf) under ethylene ga ve [N3NF]W(C2H4), which could be oxidized to yield diamagnetic {[N3NF]W(C2H 4)}OTf.