Chiral "P-N-P" ligands, $(C_{20}H_{12}O_2)PN(R)PY_2$ $[R = CHMe_2, Y = C_6H_5,$ $OC_6H_5,$ $OC_6H_4-4-Me,$ $OC_6H_4-4-OMe$ $\hspace {2mm}or\hspace {2mm} OC_6H_4-4-^tBu]$ and their allyl palladium complexes

Mandal, Swadhin K and Gowda, Nagana GA and Krishnamurthy, Setharampattu S and Stey, Thomas and Stalke, Dietmar (2005) Chiral "P-N-P" ligands, $(C_{20}H_{12}O_2)PN(R)PY_2$ $[R = CHMe_2, Y = C_6H_5,$ $OC_6H_5,$ $OC_6H_4-4-Me,$ $OC_6H_4-4-OMe$ $\hspace {2mm}or\hspace {2mm} OC_6H_4-4-^tBu]$ and their allyl palladium complexes. In: Journal of Organometallic Chemistry, 690 (3). pp. 742-750.

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Abstract

Chiral "P-N-P" ligands, $(C_{20}H_{12}O_2)PN(R)PY_2$ $[R = CHMe_2, Y = C_6H_5$ $(1), OC_6H_5 (2),$ $\hspace {2mm} OC_6H_4-4-Me (3),$ $ OC_6H_4-4-OMe (4)$ $or OC_6H_4-4-^tBu (5)]$ bearing the axially chiral 1,1'-binaphthyl-2,2'-dioxy moiety have been synthesized. Palladium allyl chemistry of two of these chiral ligands (1 and 2) has been investigated. The structures of isomeric $\eta^3$-allyl palladium complexes, $[Pd(\eta^3-1,3-R'_2-C_3H_3)\lbrace$ $\kappa^2-(racemic)-(C_{20}H_{12}O_2)PN(CHMe_2)PY_2\rbrace]$ $(PF_6) (R' = Me \hspace {2mm} or \hspace {2mm} Ph; Y = C_6H_5 \hspace {2mm}or \hspace {2mm} OC_6H_5)$ have been elucidated by high field two-dimensional NMR spectroscopy. The solid state structure of $[Pd(\eta^3-1,3-Ph_2-C_3H_3)\lbrace $ $\kappa^2-(racemic)-(C_{20}H_{12}O_2)PN(CHMe_2)PPh_2 \rbrace]$ $(PF_6)$ has been determined by x-ray crystallography. Preliminary investigations show that the diphosphazanes, 1 and 2 function as efficient auxiliary ligands for catalytic allylic alkylation but give rise to only moderate levels of enantiomeric excess.

Item Type:	Journal Article
Publication:	Journal of Organometallic Chemistry
Publisher:	Elsevier
Additional Information:	The Copyright belongs to Elsevier.
Keywords:	Chiral ‘‘P–N–P’’ ligands;g3-allyl palladium complexes;NMR spectroscopy;X-ray crystal structure;Allylic alkylation
Department/Centre:	Division of Chemical Sciences > Sophisticated Instruments Facility (Continued as NMR Research Centre) Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	17 Mar 2006
Last Modified:	19 Sep 2010 04:24
URI:	http://eprints.iisc.ac.in/id/eprint/5827

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