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Title: NNpyC- and ONpyC-Pincers as functional ligands for palladium(II) complexes and assemblies
Authors: Simayi, Rena
Hope, Eric G.
Singh, Kuldip
Cross, Warren B.
Solan, Gregory A.
First Published: 29-Sep-2017
Publisher: Elsevier
Citation: Journal of Organometallic Chemistry, 2017, 851, pp. 254-264 (11)
Abstract: The pyridyl-imine, -amine and -alcohol pro-ligands, 2-(2-MeC6H4)-6-{CMe=N(2,6-i-Pr2C6H3)}C5H3N (HL1), 2-(2-MeC6H4)-6-{CMe2NH(2,6-i-Pr2C6H3)}C5H3N (HL2) and 2-(2-MeC6H4)-6-(CMe2OH)C5H3N (HL3), each appended with an ortho-tolyl unit, have been synthesized by a combination of condensation and methylation approaches, all deriving from the common acetylpyridine precursor, 2-(2-MeC6H4)-6-(CMe=O)C5H3N. Treatment of HL1, HL2 and HL3 with Pd(OAc)2 results in cyclopalladation via sp2-CH activation of the tolyl unit to give the organometallic palladium(II) NNC- or ONC-pincer complexes (L1)Pd(OAc) (1a), (L2)Pd(OAc) (2a) and (L3)Pd(OAc) (3a). Quantitative conversion of 1a, 2a and 3a to their chloride derivatives, (L1)PdCl (1b), (L2)PdCl (2b) (L3)PdCl (3b), respectively, has been demonstrated. Intramolecular NH···Oacetate (2a) and intermolecular OH···Oacetate (3a) or OH⋯Cl (3b) hydrogen-bonding interactions are a feature of the crystal structures for 2a, 3a and 3b; notably in 3a and 3b this leads to self-assembly into dimers with differing metal···metal separations. The molecular structures for HL1, HL2, 1a, 1b and 2b are additionally reported as is full characterization data for both the pro-ligands and complexes.
DOI Link: 10.1016/j.jorganchem.2017.09.041
ISSN: 0022-328X
eISSN: 1872-8561
Version: Post-print
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © 2017, Elsevier. Deposited with reference to the publisher’s open access archiving policy.
Description: The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.
Appears in Collections:Published Articles, Dept. of Chemistry

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