A novel hemilabile calix[4],quinoline-based P,N-ligand: coordination chemistry and complex characterisation.
The synthesis of the calix[4]arene-based P,N-ligand 3 (5,11,17,23-tetra-tert-butyl-25-[(2-quinolylmethyl)oxy]-26,27,28-(mu3-phosphorustrioxy)calix[4]arene), in which the nitrogen atom-containing moiety has been introduced at the lower rim of the cavity prior to P-functionalisation, is described and its coordination properties investigated. In the crystal structure, the calix[4]-cavity adopts a cone conformation with an exo orientation of the phosphorus lone pair enabling P-N chelation. 1H, 13C, 31P and 1H{15N} HMQC NMR spectra indicated that, in complexes [PdCl(CH3)(3)] (4) and [Rh(CO)Cl(3)] (5), ligand 3 coordinates in a chelating fashion, while in cis-[PtC12(3)2] (6) and [Rh(acac)(CO)(3)] (7) it behaves as a monodentate ligand, coordinating via the phosphorus atom only. X-Ray crystal structure determinations were performed for [PdCl(CH3)(3)] (4) and cis-[PtCl2(3)2] (6). The cationic Pd complex [Pd(CH3)(CH3CN)(3)][PF5] (8) was found to be active in a CO/ethylene copolymerisation reaction. Good selectivities were observed for the Pd-catalysed allylic alkylation of cinnamyl acetate with in situ prepared catalysts. [Rh(acac)(CO)2] modified with ligand 3 catalyses the hydroformylation of 1-octene with low selectivities towards linear aldehydes. High-pressure NMR experiments on the hydrido carbonyl rhodium(3) were inconclusive, different species were formed.
Marson
Angelica
A
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands.
Ernsting
Johanneke E
JE
Lutz
Martin
M
Spek
Anthony L
AL
van Leeuwen
Piet W N M
PW
Kamer
Paul C J
PC
D000478:Alkylation; D047250:Calixarenes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009584:Nitrogen / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D011804:Quinolines / Q000737:chemistry*
D008024:Ligands; D011804:Quinolines; D047250:Calixarenes; D010758:Phosphorus; D009584:Nitrogen