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Synthesis and reactivity of trans-N,N'-dimethyl-meso-octaalkylporphyrinogen Sm(II), Eu(II) and Yb(II) complexes: Metal-based influences on the reduction of t-butyl-1,4-diazabuta-1,3-diene

Citation

Dick, AKJ and Frey, ASP and Gardiner, MG and Hilder, M and James, AN and Junk, PC and Powanusorn, S and Skelton, BW and Wang, J and Whilte, AH, Synthesis and reactivity of trans-N,N'-dimethyl-meso-octaalkylporphyrinogen Sm(II), Eu(II) and Yb(II) complexes: Metal-based influences on the reduction of t-butyl-1,4-diazabuta-1,3-diene, Journal of Organometallic Chemistry, 695, (25-26) pp. 2761-2767. ISSN 0022-328X (2010) [Refereed Article]

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DOI: doi:10.1016/j.jorganchem.2010.07.004

Abstract

Sm(II), Eu(II) and Yb(II) complexes of doubly deprotonated trans-N,N∩-dimethyl-meso-octaethylporphyrinogen were synthesised as tetrahydrofuran adducts (Sm and Eu, bis; Yb, mono) by metathetical exchange reactions of the dipotassium macrocyclic precursor complexes with the corresponding metal diiodides in tetrahydrofuran. The Sm and Eu complexes partially desolvate in non-coordinating solvents to give mono-tetrahydrofuran adducts. Subsequent reactions of the initial Eu(II) and Yb(II) complexes with 1,4-di-t-butyl-1,4-diazabuta-1,3-diene failed to yield complexes featuring the 1,4-diazabuta-1,3-diene binding to the lanthanide centres either as neutral Lewis base donors or reduced ligands, which contrasts with previous findings in the case of the analogous Sm(II) reaction. These outcomes are discussed in relation to the variety of Ln(III)每Ln(II) reduction potentials, coordination number and oxidation state dependent ionic radii of the metals and macrocycle每ancillary ligand steric interactions. The complexes were characterised by X-ray crystal structure determination, satisfactory microanalysis and NMR spectroscopy, where possible.

Item Details

Item Type:Refereed Article
Keywords:Lanthanide; Reduction chemistry; Macrocyclic ligands; 1,4-Diazabuta-1,3-diene; Crystal structure; Steric effects
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:f-Block Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Dick, AKJ (Mr Andrew Dick)
Author:Frey, ASP (Mr Alistair Frey)
Author:Gardiner, MG (Associate Professor Michael Gardiner)
Author:James, AN (Mr Adam James)
Author:Powanusorn, S (Mr Suraphan Powanusorn)
Author:Wang, J (Dr Jun Wang)
ID Code:64667
Year Published:2010
Web of Science® Times Cited:3
Deposited By:Chemistry
Deposited On:2010-08-16
Last Modified:2011-05-12
Downloads:0

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