We have been developing the cyclopentadienyl, amidinate (CPAM) ligand set as a supporting environment for groups 4 – 6 metal complexes of the general formula, (n5-C5R5)[N(R1)C(R2)N(R1)]M(X)(Y) (I). Notably, second- and third-row group 4 derivatives of I, where X = Y = Me, serve as pre-initiators for the living coordination polymerization (LCP) of α-olefins while second- and third-row group 5 and group 6 metal derivatives of I, where X = Y = Cl, function as precursors for dinuclear end-on-bridged dinitrogen complexes that can undergo facile N≡N bond cleavage and N-atom functionalization reactions involving nitrene group transfer (NGT). To date, however, control over the activation parameters for these processes has only been achieved through empirical manipulation of non-bonded steric interactions amongst the CPAM ligand substituents. This contribution will present experimental and computational results of an investigation to establish the ability to use electronic effects to influence the relative rates of different reaction pathways, molecular structures and stabilities of intermediates involved in LCP and NGT by CPAM early transition metal complexes.

Investigation of electronic effects for the amidinate ligand of CPAM early transition metal complexes as catalysts for small molecule activation and olefin polymerization

254th National Meeting (2017)

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