NDLI: Bismuth–lithium bonding in the ion pairs: $LiBiL_{2},$ where L = a porphyrin or a salen ligand

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Chisholm, Malcolm H. Durr, Christopher B. Balasanthiran, Vagulejan
Description	Author Affiliation: Balasanthiran V ( Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, USA. Chisholm@chemistry.ohio-state.edu.)
Abstract	From the reaction between $BiCl_{3}$ (1 equiv.) and $LiN(SiMe_{3})_{2}$ (4 equiv.) and $LH_{2}$ (2 equiv.), where L = a tetraphenylporphyrin, TPP, an octaethylporphyrin, OEP and phsalen in THF the title compounds have been obtained I $LiBiTPP_{2},$ II $LiBiOEP_{2},$ and IIIA $LiBi(phsalen)_{2}$ and IIIB $LiBi(phsalen)_{2}·THF.$ Crystals grown from $CH_{2}Cl_{2}–hexanes$ 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 $LiL^{−}BiL^{+}.$ 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 $toluene-d_{8}$ at 90 °C. The MALDI-MS yields weak molecular ions due to $LiBiL_{2}^{+/−}$ with more intense ions due to $BiL^{+}$ and $LiL^{−}$ in the positive and negative modes. The short $Li^{+}$ to $Bi^{3+}$ distances are comparable to those seen in Li⋯Bi compounds, such a $LiBiR_{2},$ 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 $phsalenH_{2}$ in THF gave a compound having $Li_{2}L·2THF,$ IV. Crystallographically compound IV contains two $Li^{+}$ atoms, one coordinated to five atoms $LiO_{2}N_{2}·THF.$ and the other being coordinated to three atoms, $LiO_{2}·THF.$ By $^{7}Li$ and $^{1}H$ NMR both lithium atoms share an equivalent environment.
ISSN	14779226
Issue Number	17
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-05-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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