Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

Abstract

Methyl-, Acetyl-and Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenyl-phosphino)benzylidene-S(--)-a-methylbenzylamine LigandAnkersmit, H.A.; Loken, B.H.; Kooijman, H.; Spek, A.L.; Vrieze, K.; van Koten, G. Published in:Inorganica Chimica Acta DOI:10.1016/S0020-1693(96)05307-8 Link to publication Citation for published version (APA):Ankersmit, H. A., Loken, B. H., Kooijman, H., Spek, A. L., Vrieze, K., & van Koten, G. (1996). Methyl-, Acetyland Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenylphosphino)benzylidene-S(--)-a-methyl-benzylamine Ligand. Inorganica Chimica Acta, 252, 141-155. DOI: 10.1016/S0020-1693(96)05307-8 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. (4a) shows an analogous geometry with a chelating PN ligand, a chloride atom and a methyl group, which is positioned cis to the phosphorus atom, completes the square planar surrounding. The methylpalladium and -platinum complexes reacted with CO to give the corresponding acetyl complexes. The insertion rates increased in the order C! <Br <O3SCF 3-while the re~tiou is first order in metal complex and first order in CO concentration. Complexes [ Pd(r/3-allyl) (PN) ] + Y-(Y = CI, O3SCF3) with symmetric allyl groups 2-RC3H5 (R = Me, C(O)Me), 2-MeC3Me4 and asymmetrically substituted allyi groups 2-R-C3HzM% (R ~ H, Me) have been prepared. Temperature dependent ~H, 3tp{ tH} and 13C{ tH} NMR has been used to determine the influence of the chiral ligand on the structural aspects and dynamic features. It is shown that a delicate balance between counteracting steric and electronic factors determines the type of isomer, i.e. with the P atom cis or trans to the CMe2 moiety of the asymmetric allyl group.

Neutral palladium(II) complexes with P,N Schiff-base ligands: Synthesis, characterization and application as Suzuki–Miyaura coupling catalysts

“…The remaining two angles around the palladium centre are close to the expected 90 , i.e 89.79 (6) and 89.18 (6) for C(1)ePd(1)eP(1) and C(1)ePd(1)eCl(1) respectively. These values are in good agreement with those obtained for similar complexes [31,42,43]. (10) 1.278(2) N(1)eC (2) 1.484(2) Bond angles P(1)ePd(1)eCl (1) 177.15(2) N(1)ePd(1)e(Cl (1) 93.85(5) C(1)ePd(1)eCl (1) 89.18(6) N(1)ePd(1)eP (1) 87.45(5) C(1)ePd(1)eP (1) 89.79(6) C(1)ePd (1)eN(1) 173.39 (7) 2…”

Isomeric Preference in Complexes of Palladium(II) with Chelating P,N‐Donor Ligands

“…This result is in good agreement with previous published results of similar complexes. [16,20,21] The reaction of complexes 2a-c with AgBF 4 in acetonitrile yielded the removal of the chlorido ligand but the result depends on the coordinating nature of the ligands. For complex 2a the reaction afforded the substitution of the chlorido ligand by an acetonitrile ligand keeping the position of the methyl group with respect to the chelating ligand (i.e.…”

Iminophosphine palladium catalysts for Suzuki carbonylative coupling reaction

“…Ligands 1 , 2 and 3 and Pd(II) complexes 1a , 2a and 3a were synthesized by treating 2‐(diphenylphosphino)benzaldehyde with the appropriate primary amine under argon atmosphere using a literature procedure . All compounds are very soluble in dichloromethane, chloroform, ethanol and acetone, and insoluble in n ‐hexane and diethyl ether.…”