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Metallomacrocycles as ligands: synthesis and characterisation of aluminium-bridged bisglyoximato complexes of palladium and iron

Kelley, Paul and Radlauer, Madalyn R. and Yanez, Abraham J. and Day, Michael W. and Agapie, Theodor (2012) Metallomacrocycles as ligands: synthesis and characterisation of aluminium-bridged bisglyoximato complexes of palladium and iron. Dalton Transactions, 41 (26). pp. 8086-8092. ISSN 1477-9226.

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Dialuminiummacrocycles based on bisglyoximato moieties were prepared and their coordination chemistry with Fe^II and Pd^II was investigated. The bridging aluminium centers were supported by several types of tetradentate diphenoxide diamine ligands. The nature of the ancillary ligands bound to aluminium was found to affect the overall geometry and symmetry of the metallomacrocycles. Enantiopure, chiral diphenoxide ligands based on the (R,R)-trans-1,2-diaminocyclohexane backbone afforded cleanly one metallomacrocycle isomer. The size and electronic properties of remote substituents on aluminium-bound ligands affected the binding mode and electronic properties of the central iron. A structurally characterized iron complex shows trigonal prismatic coordination mode, with phenoxide bridges between iron and aluminium. Increasing the size of the phenoxide substituents led to square bipyramidal coordination at iron. Employing p-NO_2- instead of p-tBu-substituted phenoxide as supporting ligands for aluminium caused a 0.27 V positive shift of the Fe^(III)/Fe^(II) reduction potential. These results indicate that the present synthetic approach can be applied to a variety of metallomacrocycles based on bisglyoximato motifs to affect the chemistry at the central metal.

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Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2012 Royal Society of Chemistry. Received 9th February 2012; Accepted 16th April 2012. First published on the web 14 May 2012. We thank Lawrence M. Henling for collection of XRD data and preliminary structure analysis and Dr. David E. Herbert for crystal structures of 3b and 8tBu. We are grateful to Caltech, Dow Chemical and the Caltech MURF program (AJY) for funding. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to Caltech, CHE-0639094.
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Caltech Minorities Undergraduate Research Fellowship (MURF)UNSPECIFIED
Issue or Number:26
Record Number:CaltechAUTHORS:20120713-152737041
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32441
Deposited By: Jason Perez
Deposited On:16 Jul 2012 14:50
Last Modified:03 Oct 2019 04:00

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