Creation and Function of New Election-dificient Transition Metal Chalcogenide Complexs

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We herewith summarize the results obtained under this research project.(1) A new lanthanide chemistry has been developed based on "hard" - "soft" interactions between lanthanide metals and S-donor ligands. We have isolated and structurally characterized [Li(thf)_2]_3[Yb_5S_3(S^tBu)_<12>] and [Li(tmeda)]-[YbCl_3(STsi)(tmeda)].(2) A series of Ta/Fe chalcogenide clusters have been synthesized, which have a common pentamethyl-cyclopentadienyl tantalum fragment. The reactions of "Cp^<**>Ta(S)_3Li_2" with iron chlorides produced (Et_4N)_2 [(Cp^<**>TaS_3)_2Fe] and Ta_2Fe_4E_9 (E=S,Se), the latter of which has a cluster framework closely related to the FeMo-Co structure.(3) The reactions of Cp^<**>TaCl (S^tBu) with hydrazines gave rise to Cp^<**>TaS (S^tBu) (eta^2-NMeNMeH) and Cp^<**>TaS (S^tBu) (eta^1-NNMe_2^tBu). Interestingly the latter complex contains a very rare amine-imide ligand.(4) We have carried out low temperature (100^4) solid state syntheses, in order to obtain new heterometallic sulfide clusters. For example, the reaction of [NH_4]_2 [MS_4] (M=Mo, W) with 2 equiv of [Cu(CH_3CN)_4] [PF_6] under the presence of 4 equiv of dppn (=Ph_2PCH_2PPh_2) in solid lead to the formation of [Cu_4(dppm)_4MS_4] [PF_6]_2 (M=Mo, W).(5) We have synthesized a series of W/Cu clusters with high nuclearity from the reactions between (PPh_4) - [Cp^<**>W(S)_3] and Cu(I) complexes. Examples are tetra-and octa-nuclear clusters [Cp^<**>WS_3Cu_3-Br_3]_2 and (Cp^<**>WS_3)_4Cu_4, and a 1-dimensional polymer [(Cp^<**>WS_3Ag_2)_2(mu-Br)_2]_n etc.(6) The reaction of FeCl_3 was found to promote C-S bond cleavage of [Cp^<**> Mo(StBu)_3 giving rise to a cubane cluster Cp^<**>_2Mo_2FeS_4Cl_2, which was then reacted with Li_2S_2 to generate an unusual tris-cubane cluster Cp^<**>_2Mo_2Fe_2S_4]_3(mu-S_4).