Diamidophosphines with six-membered chelates and their coordination chemistry with group 4 metals: Development of a trimethylene-methane-tethered [PN2]-type "molecular claw"

Abstract

The coordination chemistry of the phosphine-tethered diamidophosphine ligands PhP(CH2CH2CH2NHPh)2 (pr[NPN]H2) and PhP(1,2-CH2-C6H4-NHSiMe3)2 (bn[NPN]H2) featuring six-membered N-C3-P chelates was explored with group 4 metals, which allowed for the consecutive development of a new trimethylene-methane-tethered [PN2] scaffold. In the case of the propylene-linked system pr[NPN]H2, access to the sparingly soluble dibenzyl derivative pr[NPN]ZrBn2 (3-Zr) was gained, while thermally sensitive zirconium and hafnium diiodo complexes bn[NPN]MI2 (5-M, M = Zr, Hf) were isolated in the case of the benzylene-linked derivative bn[NPN]H2. Despite the related phosphine-tethered backbone architectures of both of these ligands, their group 4 complexes were found to exhibit either C1-symmetric (bn[NPN]MX2) or averaged CS-symmetric (pr[NPN]MX2) structures in solution. To restrain the overall flexibility of these systems and thereby control the properties of the resulting complexes without disrupting the six-membered chelates, the new trimethylene-methane-tethered N,N′-di-(tert-butyl)-substituted [PN2]H2 protioligand was designed. This tripodal ligand system was prepared on a gram scale and its CS-symmetric dichloro complexes [PN2]MCl2 (6-M, M = Ti, Zr, Hf) were isolated subsequently. The benzene-soluble dibenzyl derivative [PN2]ZrBn2 (7-Zr) was synthesised as well and characterised by X-ray diffraction. These results are discussed not only in conjunction with the known [NPN]-coordinated group 4 complexes incorporating five-membered chelates, but also in the context of "molecular claws" that are related to the new [PN2] tripod.