Syntheses and characterization of hepta-coordinated Group 4 amidinate complexes.

Tri-amidinate chloride complexes M[MeC(NiPr)2]3Cl [M = Zr (1), Hf (2)] have been prepared from MCl4 and lithium amidinate Li[MeC(NiPr)2]. The uncommon hepta-coordinated complexes Zr-Cl (1) and Hf-Cl (2) undergo metathesis reactions with 1 equiv. of MeLi and EtMgCl to give alkyl derivatives M[MeC(NiPr)2]3R [R = Me, M = Zr (3), Hf (4); R = Et, M = Zr (5), Hf (6)].

Synthesis, structural characterization and NMR studies of group 10 metal complexes with macrocyclic amine N-heterocyclic carbene ligands.

A series of Ni(ii), Pd(ii) and Pt(ii) complexes [ML][PF] [L = L, M = Ni (1), Pd (2), Pt (3); L = L, M = Ni (4), Pd (5), Pt (6)] and [Pt(L)(acac)] (7) have been prepared by the reactions of two tetradentate macrocyclic amine-NHC ligand precursors, [HL][PF] and [HL][PF], with Ni(OAc)·4HO, Pd(OAc) and Pt(acac) in the presence of NaOAc. Complex 7 is isolated along with 6 from the same reaction between [HL][PF] and Pt(acac). There are two atropisomers in 1-3 and two achiral conformers in 4-6.