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Synthesis, X-ray structures and redox behaviour of the group 14 bis-boraamidinates M[PhB(μ-N-t-Bu)2]2 (M = Ge, Sn) and Li2M[PhB(μ-N-t-Bu)2]2 (M = Sn, Pb)

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Konu, J., Tuononen, H., & Chivers, T. (2009). Synthesis, X-ray structures and redox behaviour of the group 14 bis-boraamidinates M[PhB(μ-N-t-Bu)2]2 (M = Ge, Sn) and Li2M[PhB(μ-N-t-Bu)2]2 (M = Sn, Pb). Canadian Journal of Chemistry, 87(3), 461-471. https://doi.org/10.1139/v08-183
Published in
Canadian Journal of Chemistry
Authors
Konu, Jari |
Tuononen, Heikki |
Chivers, Tristram
Date
2009
Discipline
Epäorgaaninen ja analyyttinen kemiaInorganic and Analytical Chemistry
Copyright
© 2009, NRC Research Press or its licensors

 
The solid-state structures of the complexes M[PhB(μ-N-t-Bu)2]2 (1a, M= Ge; 1b, M = Sn) were determined to be spirocyclic with two orthogonal boraamidinate (bam) ligands N,N′-chelated to the group 14 centre. Oxidation of 1b with SO2Cl2 afforded the thermally unstable, blue radical cation {Sn[PhB(μ-N-t-Bu)2]2}•+, identified by electron paramagnetic resonance (EPR) spectroscopy supported by density functional theory (DFT) calculations, whereas the germanium analogue 1a was inert towards SO2Cl2. The reaction between Li2[PhB(μ-N-t-Bu)2]2 and SnCl2 or PbI2 in 2:1 molar ratio in diethyl ether produced the novel heterotrimetallic complexes Li2Sn[PhB(μ-N-t-Bu)2]2 (2b) and (Et2O·Li)LiPb[PhB(μ-N-t-Bu)2]2 (2c·OEt2), respectively. By contrast, treatment of Li2[PhB(μ-N-t-Bu)2]2 with C4H8O2·GeCl2 yielded the germanium(IV) complex 1a via a redox process. The X-ray structures of 2b and 2c·THF revealed polycyclic arrangements in which one bam ligand is N,N′-chelated to the Sn(II) or Pb(II) atom and one of the Li+ cations, while the second bam ligand exhibits a unique bonding mode, bridging all three metal centres. The fluctional behaviour of 2b was investigated by variable temperature, multinuclear NMR spectroscopy. ...
Publisher
NRC Research Press
ISSN Search the Publication Forum
0008-4042
Keywords
boraamidinaatit metallikompleksit boraamidinates metal complexes
DOI
https://doi.org/10.1139/v08-183
URI

http://urn.fi/URN:NBN:fi:jyu-201511203743

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/19244146

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