Methyl-, Acetyl- and Allyl-palladium and -platinum Complexes Containing Novel Terdentate Pns and Nn's Ligands

Content Provider	Semantic Scholar
Author	Ankersmit, Hubertus A. Veldman, Nora Spek, Anthony L. Vrieze, Kees Koten, Gerard Van
Copyright Year	1996
Abstract	Abstract Palladium and platinum compounds of the composition [MX(L)]X and [M(Me)(L)]X (M  Pd, Pt; X  Cl, Br, I, O 3 SCF 3 ) have been prepared from the appropriate starting materials and the new ligands (L = N -[2-(diphenylphosphino)benzylidene]- L -methioninol (PNS-1), N -[2-(diphenylphosphino)benzylidene]-3-propylethylsulfide(PNS-2), N -{ N -[2-(diphenylphosphino)benzylidene]- D / L -methio-nyl}- tert -butylamine (PNS-3), N -{ N -[2-(pyridine)methylidene]- D / L -methionyl}- tert -butylamine (NN'S)). The single crystal X-ray determination of [PtI(PNS-3)]I ( 3cz ) (triclinic, space group P 1 (No. 2) with a=10.5298(9), b=11.5584(8), c=14.545(2) A , α=77.368(8), β=84.453(9), γ=79.720(7)° , V =1696.5(3) →A 3 , Z =2, R 155, wR 2=0.1195) showed terdentate coordination of the trifunctional PNS-3 ligand with a six-membered PN containing metallacycle and a six-membered NS containing metallacycle which is in a chair conformation. The square planar geometry is completed with an iodide atom, while the second iodide atom is non-coordinating. The methyl-palladium and -platinum complexes may occur in solution in various isomeric forms, as an equilibrium has been observed between the ionic [M(Me)( ν 3 -PNS)X and the neutral [MX(Me)( ν 2 -PNS)]. The η 3 -PNS bonded complex may occur in two conformations, i.e. with the six-membered NS containing part of the ligand in either the chair or boat form. The methyl-palladium and -platinum complexes reacted slowly with CO to form corresponding acetyl complexes, with insertion rates which increased in the order Cl 3 SCF 3 − and PNS-1 η 3 -allyl)(PNS-3)]X (X = Cl, O 3 SCF 3 ) with 2-methylallyl and 1,1,2-trimethylallyl groups have been prepared from the reaction of [PdCl( η 3 -allyl)] 2 with PNS-3. Both the η 3 -allyl and the unusual η 1 -allyl species have been identified by 1 H NMR and their dynamic properties have been investigated in CDCl 3 .
Starting Page	339
Ending Page	354
Page Count	16
File Format	PDF HTM / HTML
DOI	10.1016/S0020-1693(96)05333-9
Volume Number	252
Alternate Webpage(s)	https://pure.uva.nl/ws/files/2845100/1654_17208y.pdf
Alternate Webpage(s)	https://doi.org/10.1016/S0020-1693%2896%2905333-9
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article