219563-59-4Relevant academic research and scientific papers
Synthesis of new heterotridentate ligands comprising mixed hard-soft donor sets, and their complexation with Group 10 metals
Bhattacharyya, Pravat,Parr, Jonathan,Slawin, Alexandra M. Z.
, p. 3609 - 3614 (1998)
The new phosphorus-containing heterotridentate ligands 2-(2-Ph2P)C6H4CH=NCH(Me)CH(OH)Ph-1S,2R (HL1) and 2-(2-Ph2P)C6H4N=CHC6H4OH (HL2) were prepared by the condensation of 2-(diphenylphosphino)-benzaldehyde with 1S,2R-norephedrine (HL1) and 2-(diphenylphosphino)aniline with salicylaldehyde (HL2). The co-ordination chemistry of HL1 and HL2 with Group 10 metals was explored, together with that of the previously reported ligand 2-(2-Ph2P)C6H4CH=NC6H4OH (HL3) which is isomeric with (HL2). Compound HL1 affords cationic complexes of general formula [M(HL1)Cl]Cl, where M = Ni (1), Pd (2) or Pt (3). Spectroscopic, microanalytical and crystallography data for 1-3 confirm that deprotonation of the hydroxyl group does not occur on complexation. In contrast, both HL2 and HL3 deprotonate on complexation to form neutral species of general formula [MLCl] where L = L2, M = Ni (4), Pd (5) or Pt (6); L = L3, M = Ni (7), Pd (8) or Pt (9). The crystal structures of 4, 5, 7 and 9 confirm tridentate PNO co-ordination of the deprotonated ligands to the metal centres, forming 5- and 6-membered rings.
Palladium complexes with a tridentate PNO ligand. Synthesis of η1-allyl complexes and cross-coupling reactions promoted by boron compounds
Crociani, Bruno,Antonaroli, Simonetta,Burattini, Marcello,Paoli, Paola,Rossi, Patrizia
, p. 3665 - 3672 (2010/06/17)
The iminophosphine 2-(2-Ph2P)C6H4NCHC 6H4OH (P-N-OH) reacts with [Pd(μ-Cl)(η3- C3H5)]2 yielding [PdCl(P-N-O)] and propene. In the presence of NEt3, the reaction of P-N-OH with [Pd(μ-Cl)(η3-1-R1,3-R2C 3H3)]2 (R1 = R2 = H, Ph; R1 = H, R2 = Ph) affords the η1-allyl derivatives [Pd(η1-1-R1,3-R2C 3H3)](P-N-O)] (R1 = R2 = H: 1; R1 = H, R2 = Ph: 2; R1 = R2 = Ph: 3). In solution, the complexes 1 and 3 undergo a slow dynamic process which interconverts the bonding site of the allyl ligand. The X-ray structural analysis of 1 indicates a square-planar coordination geometry around the palladium centre with a P,N,O,-tridentate ligand and a σ bonded allyl group. The complexes [PdR(P-N-O)] (R = C6H4Me-4, CCPh) react slowly with p-bromoanisole in the presence of p-tolylboronic acid to give [PdBr(P-N-O)] and the coupling product RC6H4OMe-4. The latter reactions also proceed at a low rate under catalytic conditions. The coupling of allyl bromide with p-tolylboronic acid is catalyzed by [PdCl(P-N-O)]/K2CO3 to give 4-allyltoluene.
