Tuning the reactivity of metals held in a rigid ligand environment

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Abstract
Research on the chemistry of monoanionic aryl ligands having ortho- or bis-orthodimethylaminomethyl substituents, i.e., C6H4(CHzNMe2)-2, A, CioHgNMe2-8, B and cgH3(CH2NMe2)2-2,6, C, that form organometallic compounds with a direct M-Ca 1 o-bond, WIII be discussed. Through coordination of the N-donor site(s) of the ortho CH2NMe2 arm(s) five-meaered M-C-C-C-N chelate ring formation occurs. In particular, the rigid bis-ortho chelation of the terdentate ligand C provides the complexed metal centre with a set of unusual properties. Firstly, this ligand restricts the number of coordination sites that are available for incoming reagents and other li ands This is a situation that can frustrate the normal course of, for example, an oxidative reaction at the N donor atoms make these ligands extremely electron-rich and consequently they afford coniplexed (d8) metal centres with an enhanced nucleophilicity. Together, these features provide their complexes with unexpected and novel properties; e.g. q I-coordination of 12 to PtlI, stable NiI'I-carbon bonds, and intramolecular rearrangements involving C-H bond activation. Here, the first experiments aimed at modelling the available space for incoming reagents by a variation of the alkyl substituents at the nitrogen donor atoms will be described. bound d 53' metal centre and lead to "trapped intermediates" with a considerable stability. Secondly, the hard C and
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