Journal ArticleDOI
Structural studies on iminophosphine ligands and their palladium complexes
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The crystal and molecular structures of the iminophosphine o-(Ph2P)C6H4CH=NC6H 4OMe-4 and its palladium complexes have been determined by X-ray analysis as mentioned in this paper.Abstract:
The crystal and molecular structures of the iminophosphine o-(Ph2P)C6H4CH=NC6H4OMe-4 (1) and its palladium complexes [Pd(η3-C3H5){o-(Ph2P)C6H4CH=NC6H4OMe-p}]BF4 (2) and [Pd(η2-fn){o-(Ph2P)C6H4CH=NC6H4OMe-4}] [fn = fumaronitrile, (3)] have been determined by X-ray analysis. In the free ligand (1), the planar imino group of E configuration is oriented, relative to the PPh2 unit, so that the CH=N hydrogen atom points towards phosphorus, with the nitrogen atom on the opposite side. In (2) and (3) the iminophosphine behaves as a P,N-chelate ligand, this coordination mode being achieved by the imino group rotation of 169.3 ° and 145.3 °, respectively, around its bond with the ortho disubstituted phenyl ring. Complex (2) shows a structural disorder with two different orientations of the allyl ligand. The trigonal planar coordination around the central metal in complex (3) involves the P- and N-donor atoms of (1) and the η2-bound olefin, with a marked lengthening of the olefinic carbon-carbon bond. In both the complexes, the chelate six-membered ring of the iminophosphine with palladium is not coplanar with the N-Pd-P coordination plane, the imino carbon atom and the ortho disubstituted phenyl group lying on the same side out of the N-Pd-P plane, whereas the N-substituent and one of the PPh2 groups are on the opposite side. The 1H-n.m.r. spectra at low temperatures of (2) and (3), and of [Pd(η2-tmetc){o-(Ph2P)C6H4CH=NCMe3}] [tmetc = tetramethyl ethylenetetracarboxylate, (4)] are interpreted on the basis of a non-rigid conformation of the chelate iminophosphine, which undergoes a fast dynamic process whereby the N- and P-substituents move above and below the coordination plane.read more
Citations
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Journal ArticleDOI
Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins
TL;DR: An overview of the general features of electron-poor olefin stabilized palladium(0) complexes bearing labile and hemi-labile ancillary ligands is presented in this paper.
Journal ArticleDOI
Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η2‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes
TL;DR: In this paper, the authors show that in the presence of an activated olefin (ol = dmfu, fn), the Pd-N ligand site exchange can be represented as a pre-equilibrium step.
Journal ArticleDOI
Preparation and catalytic properties of palladium(0) and rhodium(I) complexes containing new chiral P, N-ligands derived from carbohydrates
TL;DR: In this paper, the synthesis of palladium(0) and rhodium(I) complexes of respective formula [Pd(P,N-chelate)(fumarodinitrile)] and [Rh(1,5-cyclooctadiene)(P, N-Chelate)]BF4 was performed.
Journal ArticleDOI
Kinetics and mechanism of regioselective amination of the 1-phenylallyl group in cationic palladium(II) complexes bearing bidentate ligands
TL;DR: In this article, the steric and electronic properties of both the amine HY and the ligand L−L′ were investigated for fumaronitrile cationic complexes, and the amination rates were found to depend on the k 2 [HY] term for 2a and 3a, and on the sum k 2[HY]-k 3 [HY]- 2 for the other complexes.
Journal ArticleDOI
Conformational flexibility and molecular dynamics of cationic diolefin-rhodium(I) complexes with iminophosphine ligands
TL;DR: In this article, a conformational change of the iminophosphine ligand is proposed which inverts the position of the six-membered chelate ring relative to the NRhP coordination plane.
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Journal ArticleDOI
Carbostannylation of alkynes catalyzed by an iminophosphine-palladium complex
Journal ArticleDOI
An iminophosphine-palladium catalyst for cross-coupling of aryl halides with organostannanes
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