Organo-palladium(II) complexes bearing unsymmetrical N,N,N-pincer ligands: synthesis, structures and oxidatively induced coupling reactions

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Wright, L.A., Hope, E.G., Solan, G.A., Cross, W.B. ORCID: 0000-0001-6277-400X and Singh, K., 2015. Organo-palladium(II) complexes bearing unsymmetrical N,N,N-pincer ligands: synthesis, structures and oxidatively induced coupling reactions. Dalton Transcations, 44 (16), pp. 7230-7241. ISSN 1477-9226

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Official URL: http://dx.doi.org/10.1039/c5dt00216h

Abstract

The 2-(2'-aniline)-6-imine-pyridines, 2-(C6H4--2'-NH2)-6-(CMe=NAr)C5H3 N (Ar = 4-i-PrC6H4 (HL1a), 2,6-i-Pr2C6H3 (HL1b)), have been synthesised via sequential Stille cross-coupling, deprotection and condensation steps from 6-tributylstannyl-2-(2-methyl-1,3-dioxolan-2-yl)pyridine and 2-bromonitrobenzene. The palladium(II) acetate N,N,N-pincer complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}Pd(OAc)] (Ar = 4-i-PrC6H4 (1a), 2,6-i-Pr2C6H3 (1b)), can be prepared by reacting HL1 with Pd(OAc) 2 or, in the case of 1a , more conveniently by the template reaction of ketone 2-(C6H4-2'-NH2)-6-(CMe=O)C5H3N, Pd(OAc)2 and 4-isopropylaniline; ready conversion of 1 to their chloride analogues, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdCl] (Ar = 4-i-PrC6H4 (2a), 2,6-i-Pr2C6H3 (2b)), has been demonstrated. The phenyl-containing complexes, [{2-(C6H4-2'-NH)-6-(CMe=NAr)C5H3N}PdPh] (Ar = 4-i-PrC6H4 (3a), 2,6-i-Pr2C6H3 (3b)), can be obtained by treating HL1 with (PPh3)2 PdPh(Br) in the presence of NaH or with regard to 3a, by the salt elimination reaction of 2a with phenyllithium.

Item Type:

Journal article

Publication Title:

Dalton Transcations

Creators:

Wright, L.A., Hope, E.G., Solan, G.A., Cross, W.B. and Singh, K.

Publisher:

Royal Society of Chemistry

Place of Publication:

Cambridge

Date:

2015