744161-88-4Relevant academic research and scientific papers
Low-dimensional architectures in isomeric cis-ptcl2{PH2pch2n(AR)CH2pph2} complexes using regioselective-n(aryl)-group manipulation
De’Ath, Peter,Elsegood, Mark R. J.,Sanchez-Ballester, Noelia M.,Smith, Martin B.
, (2021/12/04)
The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to PtII, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph2PCH2N(Ar)CH2PPh2 [1a-e; Ar = C6H3(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands Ph2PCH2N{CH2C(O)NH(Ar)}CH2PPh2 [2a-e; Ar = C6H3(Me)(OH)], were synthesised by reaction of Ph2PCH2OH and the appropriate amine in CH3OH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines Ph2PCH2N{CH2C(O)NH(Ar)}CH2PPh2 [2f, Ar = 3-C6H4(OH); 2g, Ar = 4-C6H4(OH)] and Ph2PCH2N(Ar)CH2PPh2 [3, Ar = 3-C6H4(OH)] were also prepared for comparative purposes. Reactions of 1a-e, 2a-g, or 3 with PtCl2(η4-cod) afforded the corresponding square-planar complexes 4a-e, 5a-g, and 6 in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (1H,31P{1H}, FT-IR) and analytical techniques. Single crystal X-ray structures have been determined for 1a, 1b?CH3OH, 2f?CH3OH, 2g, 3, 4b?(CH3)2SO, 4c?CHCl3, 4d??Et2O, 4e??CHCl3??CH3OH, 5a??Et2O, 5b, 5c??H2O, 5d?Et2O, and 6?(CH3)2SO. The free phenolic group in 1b?CH3OH, 2f?CH3OH,2g, 4b?(CH3)2SO, 5a??Et2O, 5c??H2O, and 6?(CH3)2SO exhibits various intra- or intermolecular O-H???X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.
New κ3-PNN′- and κ4-PNN′O- polydentate ligands: Synthesis, coordination and structural studies
Elsegood, Mark R.J.,Sanchez-Ballester, Noelia M.,Smith, Martin B.
, p. 115 - 121 (2012/02/02)
The three-step synthesis of new mixed P/N/N′/O-donor ligands C 6H3(OH){2-NHC(O)CH2NCHC6H 4PPh2}(4-CH3) 3a·HH and C 6H4(OH){3-NHC(O)CH2NCHC6H 4PPh2} 3b·HH, by Schiff base condensation of the 1° amines C6H3(OH){2-NHC(O)CH2NH 2}(4-CH3) 2a or C6H4(OH){3-NHC(O) CH2NH2} 2b with C6H4(CHO)(2-PPh 2) in refluxing EtOH, is described. Reaction of 1 equiv. of 3a·HH or 3b·HH with MCl2(cod) (M = Pt, Pd; cod = cycloocta-1,5-diene) affords the κ2-PN-chelate complexes MCl2(3a·HH) (M = Pd 4a; M = Pt 4b) and MCl 2(3b·HH) (M = Pt 4c). The dichlorometal(II) complexes 4d and 4e, bearing instead a pendant 4-phenolic group, were similarly prepared (in >90% yield). Chloro-bridge cleavage of [Pd(μ-Cl)(η3-C 3H5)]2 with 3a·HH or 3b·HH gave the monocationic κ2-PN-chelate complexes [Pd(η3- C3H5)(3a·HH)]Cl 5a or [Pd(η3-C 3H5)(3b·HH)]Cl 5b, respectively. Elimination of cod, and single CH3 protonation, from Pt(CH3) 2(cod) upon reaction with 1 equiv. of 3a·HH or 3b·HH in C7H8 at room temperature afforded the neutral complexes C6H3(OH){2-NC(O)CH2NCHC6H 4PPh2Pt(CH3)}(4-CH3) 6a and C 6H4(OH){3-NC(O)CH2NCHC6H 4PPh2Pt(CH3)} 6b, respectively bearing a monoanionic (3a·H- or 3b·H-) κ3-PNN′-tridentate ligand. Amide and phenol deprotonation were readily achieved, using KOtBu as base, to give high yields of the κ4-PNN′O-tetradentate complexes C6H 3(O){2-NC(O)CH2NCHC6H4PPh 2Pd}(4-CH3) 7a and C6H3(O){2-NC(O) CH2NCHC6H4PPh2Pt}(4-CH3) 7b bearing the dianionic ligand 3a2-. All new compounds have been characterised by multinuclear NMR, FTIR, mass spectroscopy and microanalysis. Single crystal X-ray studies have been performed on compounds 1b·1.5CH2Cl2, 3b·HH·0.5Et 2O, 6b·CHCl3 and 7b·0.5Et2O.
