| The first portion of this thesis deals with the reactivity of M(,2)(OR)(,6) compounds with cyanamide, R(,2)'NC(TBOND)N. The aims of the research were to determine what factors influence adduct formation versus metathesis type reactions. In addition to this the reactivity of the cyanamide ligand was studied once bound to the dimetal center. It was found that 1:1 adducts are formed with Mo(,2)(ONp)(,6), Np = CH(,2)-t-Bu, where the cyanamide bridges the dimetal center parallel to the metal metal bond. In contrast to the chemistry found for Mo(,2)(ONp)(,6), 3:1 adducts are formed with W(,2)(ONp)(,6)(HNMe(,2))(,2) giving W(,2)(ONp)(,6)(Me(,2)NCN)(,3) where 2 cyanamides bridge parallel to the M-M vector and the third cyanamide is (pi) bound through the C(TBOND)N unit to one W atom. W(,2)(O-t-Bu)(,6) gives a metathesis type reaction forming (t-BuO)(,3)W(TBOND)CNR(,2) and (t-BuO)(,3)W(TBOND)N. It was found that the metathesis type reaction for (RO)(,3)W(TBOND)CR compounds may be reversed by addition of C(TBOND)O leading to products derived from carbyne- carbyne coupling.;Reactions of MoN(OR)(,3) and Mo(OR)(,6) without added alcohol give Mo(,4)(N)(,2)(OR)(,12) compounds which are similar to the 1:1 adducts of Mo(,2)(OR)(,6) compounds and cyanamide. A metathesis type reaction also occurs with (t-BuO)(,3)MoN and W(,2)(O-t-Bu)(,6) to give nitride transfer from Mo to W.;The second portion of this thesis reports studies of reactions involving (RO)(,3)M(TBOND)N and M(,2)(OR)(,6) compounds in order to compare the reactivity of the M(TBOND)N unit with the C(TBOND)N unit. MoN(OR)(,3) and WN(OR)(,3) compounds were synthesized and the M-N unit was found to be reactive toward alcohol. Reaction of (RO)(,3)M(TBOND)N compounds with M(,2)(OR)(,6) compounds in the presence of HOR leads to the formation of M(,2)M'(NH)(OR)(,10). A series of imido capped compounds were formed where M(,2)M' = Mo(,3), Mo(,2)W, W(,2)Mo, and W(,3). |
