title: Highly Electron-Rich β-Diketiminato Systems: Synthesis and Coordination Chemistry of Amino-Functionalized "N-nacnac" Ligands.
abstract: The synthesis of a class of electron-rich amino-functionalized β-diketiminato (N-nacnac) ligands is reported, with two synthetic methodologies having been developed for systems bearing backbone NMe2or NEt2groups and a range of N-bound aryl substituents. In contrast to their (Nacnac)H counterparts, the structures of the protio-ligands feature the bis(imine) tautomer and a backbone CH2group. Direct metalation with lithium, magnesium, or aluminium alkyls allows access to the respective metal complexes through deprotonation of the methylene function; in each case X-ray structures are consistent with a delocalized imino-amide ligand description. Transmetalation using lithium N-nacnac complexes is then exploited to access p- and f-block metal complexes, which allow for like-for-like benchmarking of the N-nacnac ligand family against their more familiar Nacnac counterparts. In the case of SnII, the degree of electronic perturbation effected by introduction of the backbone NR2groups appears to be constrained by the inability of the amino group to achieve effective conjugation with the N2C3heterocycle. More obvious divergence from established structural norms is observed for complexes of the harder YbIIion, with azaallyl/imino and even azaallyl/NMe2coordination modes being demonstrated by X-ray crystallography.
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Dinh Cao Huan
authors.initials: DCH
authors.lastname: Do
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Ailsa
authors.initials: A
authors.lastname: Keyser
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Andrey V
authors.initials: AV
authors.lastname: Protchenko
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria, 3800, Australia.
authors.forename: Brant
authors.initials: B
authors.lastname: Maitland
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria, 3800, Australia.
authors.forename: Indrek
authors.initials: I
authors.lastname: Pernik
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Haoyu
authors.initials: H
authors.lastname: Niu
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Eugene L
authors.initials: EL
authors.lastname: Kolychev
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Arnab
authors.initials: A
authors.lastname: Rit
authors.affiliation: SPMS-CBC, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
authors.forename: Dragoslav
authors.initials: D
authors.lastname: Vidovic
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria, 3800, Australia.|Present address: EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, UK.
authors.forename: Andreas
authors.initials: A
authors.lastname: Stasch
authors.affiliation: School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria, 3800, Australia.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones
authors.affiliation: Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, OX1 3QR, Oxford, UK.
authors.forename: Simon
authors.identifier: http://orcid.org/0000-0001-9998-9434
authors.initials: S
authors.lastname: Aldridge
keywords: coordination chemistry; electron-rich compounds; ligand design; main group chemistry; nacnac ligands