title: Subtle differences between Zr and Hf in early/late heterobimetallic complexes with cobalt.
abstract: The phosphinoamide-linked Co/Hf complexes ICo(Ph(2)PN(i)Pr)(3)HfCl (4), ICo((i)Pr(2)PNMes)(3)HfCl (5), and ICo((i)Pr(2)PN(i)Pr)(3)HfCl (6) have been synthesized from the corresponding tris(phosphinoamide)HfCl complexes (1-3) for comparison with the recently reported tris(phosphinoamide) Co/Zr complexes. Very minor structural and electronic differences between the Zr and Hf complexes were found when the N-(i)Pr-substituted phosphinoamide ligands [Ph(2)PN(i)Pr](-) and [(i)Pr(2)PN(i)Pr](-) were utilized. The reduction products [(THF)(4)Na-{N(2)-Co(Ph(2)PN(i)Pr)(3)HfCl}(2)]Na(THF)(6) (7) and N(2)-Co((i)Pr(2)PN(i)Pr)(3)Hf (9) are also remarkably similar to the corresponding Zr/Co analogues. In the case of Hf/Co and Zr/Co complexes linked by the N-Mes ligand [(i)Pr(2)PNMes](-) (Mes = 2,4,6-trimethylphenyl), however, more pronounced differences in structure, bonding, and reactivity are observed. While differences associated with 5 are still modest, larger variations are observed when comparing the two-electron reduction product [N(2)-Co((i)Pr(2)PNMes)(3)Hf-X][Na(THF)(5)] (8) with its Zr congener. In addition to structural and spectroscopic differences, vastly different reactivity is observed, with 8 undergoing one-electron oxidation to form ClHf(MesNP(i)Pr(2))(3)CoN(2) (11) in the presence of MeI, while a two-electron oxidative addition process occurs in a similar reaction with the Zr derivative. The activity of 5 toward Kumada coupling was investigated, finding significantly diminished activity in comparison to Co/Zr complexes.
authors.affiliation: Department of Chemistry, Brandeis University, 415 South Street, Waltham, Massachusetts 02454, USA.
authors.forename: Vinay N
authors.initials: VN
authors.lastname: Setty
authors.forename: Wen
authors.initials: W
authors.lastname: Zhou
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Christine M
authors.initials: CM
authors.lastname: Thomas