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The synthesis and characterization of triazenido complexes of the group IV metals zirconium and hafnium is reported. The reaction of the group IV pentafulvene complexes Cp*(π–η5:σ–η1-pentafulvene)-zirconium(IV) and -hafnium(IV)chlorides with the sterically demanding 2,6-dimesitylphenyl azide results in the insertion of the γ-nitrogen atom of the ligand precursor into the polarized M–Cexo (Cexo: exocyclic carbon atom) bond of the pentafulvene ligand, forming a formal Cp,N,N tridentate ligand system. The molecular structures of the furnished complexes reveal the rare κ1 N coordination of the γ-nitrogen atom to the zirconium or hafnium center along with a localized Nα–Nβ double bond. Unusually, in one case, the ligand system shows additional coordination of the α-nitrogen atom to the central metal atom and well-balanced N–N distances, thus, forming the chelating κ2 N,N coordination mode of the triazenido ligand. The potential use of the formed complexes as precursors for cationic group IV cationic complexes was investigated by reaction with methyl lithium.

Abstract. Springback or shape change has been one of the major challenges in sheet metal fabrication, particularly with increase application of high strength steel (HSS) and aluminum alloys in automotive stamping. Springback, an elastic material recovery after the unloading of stamping tools, causes variations and inconsistencies of final part dimensions. Minor or mild springback usually can be corrected in the re-strike process. Excessive springback must be corrected so the part will be produced within the given design tolerance and dimension. The commonly used Spring Forward approaches and shape compensations such as overcrown and over-bending are proven effective to alleviate excessive springback. To enhance these approaches, a new strategy of Die Face Engineering (DFE) based processing is proposed to quickly and easily to achieve the maximum allowable compensation using the under cut (or die lock) as the primary criteria.The implementation of the die face compensation through iterative FEA calculation, automatic surface mapping, projection and manual morphing are crucial to meet production environment requirements in terms of generating NC quality CAD surfaces of the compensated or morphed die face. In this paper, the strategy of the die face compensation with the consideration of the under cut criteria is presented. The implementation of various processes to enable user to perform the die face compensation task in a production environment is also discussed. Finally, two examples are shown to demonstrate the implementation of the proposed springback compensation scheme based on the combined CAE/CAD methodology.

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