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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/11873

Title: Unusual reactivity of a sterically hindered diphosphazane ligand, EtN{P(OR)(2)}(2), (R = C6H3(Pr-i)(2)-2,6) towards (eta(3)-allyl)palladium precursors
Authors: KRISHNA, H
KRISHNAMURTHY, SS
NETHAJI, M
MURUGAVEL, R
PRABUSANKAR, G
Keywords: ray crystal-structure
n-p ligands
reductive elimination
palladium complexes
nucleophilic-attack
phosphine complexes
diaryl ethers
zerovalent palladium
selective cleavage
bicyclic alkenes
Issue Date: 2007
Publisher: ROYAL SOC CHEMISTRY
Citation: DALTON TRANSACTIONS, (27), 2908-2914
Abstract: The reactivity of (eta(3)-allyl) palladium chloro dimers [(1-R-eta(3)-C3H4)PdCl](2) ( R = H or Me) towards a sterically hindered diphosphazane ligand [EtN{P(OR)(2)}(2)] (R = C6H3(Pr-i)(2)-2,6), has been investigated under different reaction conditions. When the reaction is carried out using NH4PF6 as the halide scavenger, the cationic complex [(1-R-eta(3)-C3H4)Pd{EtN(P(OR)(2))(2)}] PF6 (R = H or Me) is formed as the sole product. In the absence of NH4PF6, the initially formed cationic complex, [(eta(3)-C3H5)Pd{EtN(P(OR)(2))(2)}]Cl, is transformed into a mixture of chloro bridged complexes over a period of 4 days. The dinuclear complexes, [(eta(3)-C3H5)Pd-2(mu-Cl)(2){P(O)(OR)(2)}{P(OR)(2)(NHEt)}] and [Pd(mu-Cl){P(O)(OR)(2)}{P(OR)(2)(NHEt)}](2) are formed by P-N bond hydrolysis, whereas the octa-palladium complex [(eta(3)-C3H5)(2-Cl-eta(3)-C3H4)Pd-4(mu-Cl)(4)(mu-EtN{P(OR)(2)}(2))] (2), is formed as a result of nucleophilic substitution by a chloride ligand at the central carbon of an allyl fragment. The reaction of [EtN{P(OR)(2)}(2)] with [(eta(3)-C3H5)PdCl](2) in the presence of K2CO3 yields a stable dinuclear (eta(3)-allyl)palladium(I) diphosphazane complex, [(eta(3)-C3H5)[mu-EtN{P(OR)(2)}(2)Pd2Cl] which contains a coordinatively unsaturated T-shaped palladium center. This complex exhibits high catalytic activity and high TON's in the catalytic hydrophenylation of norbornene.
URI: http://dx.doi.org/10.1039/b703308g
http://dspace.library.iitb.ac.in/xmlui/handle/10054/11873
http://hdl.handle.net/10054/11873
ISSN: 1477-9226
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