Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 17, 2015
Previous Article Next Article

Bismuth–lithium bonding in the ion pairs: LiBiL2, where L = a porphyrin or a salen ligand

Author affiliations

Abstract

From the reaction between BiCl3 (1 equiv.) and LiN(SiMe3)2 (4 equiv.) and LH2 (2 equiv.), where L = a tetraphenylporphyrin, TPP, an octaethylporphyrin, OEP and phsalen in THF the title compounds have been obtained I LiBiTPP2, II LiBiOEP2, and IIIA LiBi(phsalen)2 and IIIB LiBi(phsalen)2·THF. Crystals grown from CH2Cl2–hexanes are colored; I (green), II (red-purple) and IIIA and IIIB (red-orange). The molecular structures of compound I, IIIA and IIIB were determined by single-crystal X-ray crystallography and are shown to have short Li⋯Bi bonds of distance 2.8 Å involving the LiLBiL+. Compound IIIA shows a slipped structure involving Li to two oxygens and a Li⋯Bi distance of 3.1 Å. Compounds IIIA and IIIB undergo a rapid reversible exchange in toluene-d8 at 90 °C. The MALDI-MS yields weak molecular ions due to LiBiL2+/− with more intense ions due to BiL+ and LiL in the positive and negative modes. The short Li+ to Bi3+ distances are comparable to those seen in Li⋯Bi compounds, such a LiBiR2, and are comparable to those seen by Pyykkö (P. Pyykkö, J. Phys. Chem. A, 2015, 119, 2326; P. Pyykkö and M. Atsumi, Chem. – Eur. J., 2009, 15, 186; P. Pyykkö and M. Atsumi, Chem. – Eur. J., 2009, 15, 12770) for Li–Bi bonds. These can be seen to be involving Bi6s6p hybrid lone-pairs to Li+ atoms. The lithium bis(bistrimethylsilyl)amide (2 equiv.) and phsalenH2 in THF gave a compound having Li2L·2THF, IV. Crystallographically compound IV contains two Li+ atoms, one coordinated to five atoms LiO2N2·THF. and the other being coordinated to three atoms, LiO2·THF. By 7Li and 1H NMR both lithium atoms share an equivalent environment.

Graphical abstract: Bismuth–lithium bonding in the ion pairs: LiBiL2, where L = a porphyrin or a salen ligand

Back to tab navigation

Supplementary files

Article information


Submitted
19 Jan 2015
Accepted
19 Mar 2015
First published
07 Apr 2015

Dalton Trans., 2015,44, 8205-8213
Article type
Paper

Bismuth–lithium bonding in the ion pairs: LiBiL2, where L = a porphyrin or a salen ligand

V. Balasanthiran, M. H. Chisholm and C. B. Durr, Dalton Trans., 2015, 44, 8205
DOI: 10.1039/C5DT00256G

Social activity

Search articles by author

Spotlight

Advertisements