Hexafluorosilicate and tetrafluoroborate coordination to lead(II) di- and tri-imine complexes – Unusual fluoroanion coordination modes. (8th January 2015)

• Record Type: Journal Article
• Authors: Burt, Jennifer; Grantham, William; Levason, William; Light, Mark E.; Reid, Gillian
• Is Part Of: Polyhedron. Volume 85(2015)
• Page Start: 530
• Page End: 536
• Publication Date: 2015-01-08
• Subjects: Lead(II) -- Hexafluorosilicate -- Tetrafluoroborate -- Diimine -- Triimine; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2014.09.016
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: Diimine complexes of Pb(BF4 )2 and Pb(SiF6 ) are reported and their structures show significant fluoroanion coordination, leading to highly irregular geometries at Pb(II). Abstract: Lead(II) tetrafluoroborate and hexafluorosilicate complexes with 2, 2′-bipyridyl, 1, 10-phenathroline and 2, 2′:6′, 2″-terpyridyl have been prepared from the ligand and lead salt in aqueous/MeCN. Crystal structures are reported for [Pb(bipy)2 (SiF6 )], [Pb(phen)2 (SiF6 )] and [Pb(bipy)2 (BF4 )2 ] which are dinuclear with each lead coordinated " cis " to the two diimines and with the bridging fluoroanions completing eight or nine-coordination. [Pb(phen)2 (BF4 )2 ] is eight-coordinate and mononuclear with " cis " diimines and two κ 2 -BF4 − groups. [Pb(phen)2 (H2 O)2 (SiF6 )] is also mononuclear with a κ 2 -SiF6 2− group and two coordinated water molecules. Reaction of Pb(BF4 )2 with 2, 2′:6′, 2″-terpyridyl gave only [Pb(terpy)3 ][BF4 ]2, but Pb(SiF6 ) produced [Pb(terpy)(H2 O)(SiF6 )], which is a chain polymer with bridging SiF6 2− groups and significant π-stacking of the imine rings. The work has identified a number of coordination modes of the SiF6 2− anion, which has been little used in coordination chemistry but proves to be versatile and also stable (to decomposition/hydrolysis).