Palladium(ii) allyl complexes of chiral diphosphazane ligands: ambident coordination behaviour and stereodynamic studies in solutionOrganometallic chemistry of diphosphazanes. Part 17.11g.Electronic supplementary information (ESI) available: NMR and crystallographic data, stereodynamic behaviour schemes. See http://www.rsc.org/suppdata/dt/b2/b207447h/

Mandal, Swadhin K. ; Nagana Gowda, G. A. ; Krishnamurthy, Setharampattu S. ; Nethaji, Munirathinam (2003) Palladium(ii) allyl complexes of chiral diphosphazane ligands: ambident coordination behaviour and stereodynamic studies in solutionOrganometallic chemistry of diphosphazanes. Part 17.11g.Electronic supplementary information (ESI) available: NMR and crystallographic data, stereodynamic behaviour schemes. See http://www.rsc.org/suppdata/dt/b2/b207447h/ Dalton Transactions (5). pp. 1016-1027. ISSN 1477-9226

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Official URL: http://doi.org/10.1039/B207447H

Related URL: http://dx.doi.org/10.1039/B207447H

Abstract

The chemistry of η3-allyl palladium complexes of pyrazolyl substituted diphosphazane ligands, Ph2P(E)N(R)PPh(N2C3HMe2-3,5) [E = lone pair, R = CHMe2 (1); E = lone pair, R = (S)-*CHMePh (2); E = S, R = CHMe2 (3)] bearing a stereogenic phosphorus centre has been investigated and the complexes, [Pd(η3-1,3-R′2-C3H3){κ2-Ph2P(E)N(R)PPh(N2C3HMe2-3,5)}](PF6) [E = lone pair or sulfur; R = CHMe2 or (S)-*CHMePh; R′ = H, Me or Ph; 4–13], have been isolated. Detailed NMR studies reveal that these complexes exist as a mixture of isomers in solution. The structures of four complexes have been determined by X-ray crystallography and only one isomer is observed in the solid state in each case. The allyl complexes formed by ligands 1 and 2 display a P,N-coordination mode except the 1,3-diphenyl allyl complex, [Pd(η3-1,3-Ph2-C3H3){κ2-Ph2PN(CHMe2)PPh(N2C3HMe2-3,5)}](PF6) (8), which shows the presence of both P,N- and P,P-coordinated isomers in solution with the former predominating. On the other hand, the complexes bearing the diphosphazane monosulfide ligand 3 display P,S-coordination. Two-dimensional phase sensitive 1H–1H NOESY and ROESY measurements indicate that several of the above allyl palladium complexes undergo syn–anti and/or cis–trans isomerization in solution through an η1-intermediate formed by the opening of the η3-allyl group selectively at the trans position with respect to the phosphorus centre. Preliminary investigations show that the diphosphazanes (1 and (SR)-2) function as efficient auxiliary ligands for catalytic allylic alkylation reactions but lead to only low levels of enantiomeric excess.

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