NDLI: Lead(II) nitrate and hexafluorosilicate complexes with neutral diphosphine coordination

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Reid, Gillian Burt, Jennifer Levason, William Grantham, William
Description	Author Affiliation: Burt J ( School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK. wxl@soton.ac.uk.)
Abstract	Rare examples of phosphine complexes of lead(II) are reported. The reaction of $Pb(NO_{3})_{2}$ with $Me_{2}P(CH_{2})_{2}PMe_{2},$ $o-C_{6}H_{4}(PMe_{2})_{2}$ or $Et_{2}P(CH_{2})_{2}PEt_{2}$ (L–L) in $H_{2}O/MeCN$ gave white $[Pb(L–L)(NO_{3})_{2}],$ irrespective of the ratio of reagents used. The X-ray structures of $[Pb\{Me_{2}P(CH_{2})_{2}PMe_{2}\}(NO_{3})_{2}]$ and $[Pb\{o-C_{6}H_{4}(PMe_{2})_{2}\}(NO_{3})_{2}]$ reveal chelating diphosphines and $κ^{2}-NO_{3}^{−}$ groups occupying one hemisphere about the lead centre with single oxygen bridges to two further nitrate groups from neighbouring molecules completing a distorted eight-coordinate geometry. Using $Pb(SiF_{6})·2H_{2}O$ produced $[Pb\{o-C_{6}H_{4}(PMe_{2})_{2}\}(H_{2}O)(SiF_{6})]·H_{2}O$ which has a chelating diphosphine, the water molecule and a coordinated $SiF_{6}^{2−}$ group (which could be described as either $κ^{1}-$ or asymmetric $κ^{3}-coordinated$ to the lead), with further Pb–F interactions to neighbouring molecules producing a chain polymer structure. The structure of $[Pb\{o-C_{6}H_{4}(PMe_{2})_{2}\}(DMF)_{2}(SiF_{6})]·DMF$ was also determined and contains dimers with fluorosilicate bridges. Adventitious oxygen readily form diphosphine dioxide complexes, and the structures of $[Pb\{Et_{2}(O)P(CH_{2})_{2}P(O)Et_{2}\}_{2}(NO_{3})_{2}]$ and $[Pb\{Me_{2}P(CH_{2})_{2}PMe_{2}\}\{Me_{2}(O)P(CH_{2})_{2}P(O)Me_{2}\}][BF_{4}]_{2}·½MeNO_{2}$ produced in this way were determined. The former contains eight-coordinate lead with $κ^{2}-NO_{3}^{−}$ groups and bridging diphosphine dioxides, which results in an infinite polymer. In the latter the diphosphine is chelated but the diphosphine dioxide bridges between Pb(II) centres, with coordinated $BF_{4}^{−}$ groups completing a very distorted ten-coordinate moiety. Attempts to isolate similar complexes with $o-C_{6}H_{4}(PPh_{2})_{2}$ or $o-C_{6}H_{4}(AsMe_{2})_{2}$ were unsuccessful.
ISSN	14779226
Issue Number	25
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-07-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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