Synthesis of a chelating hexadentate ligand with a P3N3 donor set. Crystal and molecular structure of [OC-6-22]-[Co{(RP*,RP*,RP*)-CH3C(CH2PPhC6H4NH2-2)3}](PF6)3.

摘要: The first structurally authenticated example of a hexadentate chelating tertiary phosphine in which all six donors are bound to single metal centre is described. multidentate ligand (RP*,RP*,RP*)- and (RP*,RP*,SP*)-CH3C(CH2PPhC6H4NH2-2)3 has been prepared 80% yield via the reaction five equivalents sodium (2-aminophenyl)phenylphosphide (generated situ from (2-aminophenyl)phenylphosphine thf) with 1,1,1-tri(bromomethyl)ethane thf. diastereomeric mixture complexed cobalt(III) resulting pair complexes, viz. [Co{(RP*,RP*,RP*)-CH3C(CH2PPhC6H4NH2-2)3}]Cl3 [CoCl{(RP*,RP*,SP*)-CH3C(CH2PPhC6H4NH2-2)3}]Cl2, separated by ion exchange chromatography. structure former (as corresponding hexafluorophosphate salt) confirmed X-ray crystallography clearly shows P3N3 coordinated centre. related internal N terminal diphenylphosphino groups, CH3C(CH2NHC6H4PPh2-2)3, also synthesised, albeit low yield, [Li(tmeda)][2-NHC6H4PPh2] (2-aminophenyl)diphenylphosphine, n-butyllithium tmeda diethyl ether) 1,1,1-tri(iodomethyl)ethane No formation observed when either Na[2-PPhC6H4NH2] or reacted tripodal substrate 1,1,1-tris(tolyl-4-sulfonyloxymethyl)ethane Rather P-methyloxetane (±)-[3-{(2-aminophenyl)phenylphosphinomethyl}]-3-methyloxetane sulfonamide 2-(4-CH3C6H4SO2)NHC6H4PPh2 N-methyloxetane [3-{(2-diphenylphosphinophenyl)aminomethyl}]-3-methyloxetane have isolated respective reactions. an analysis platinum(II) complex trans-[PtCl(CH3){2-PPh2C6H4NH(SO2C6H4CH3-4)}2].