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Lanthanide(III) and group 13 metal ion complexes of tripodal amino phosphinate ligands

TitleLanthanide(III) and group 13 metal ion complexes of tripodal amino phosphinate ligands
Publication TypeJournal Article
Year of Publication2006
AuthorsKovacs, MS, Monga, V, Patrick, BO, Orvig, C
JournalDalton Transactions
Pagination31-38
Type of ArticleArticle
ISBN Number1477-9226
KeywordsACID, BEARING, CIRCULARLY-POLARIZED LUMINESCENCE, CONTRAST AGENTS, MAGNETIC-RESONANCE, NMR, RELAXOMETRY
Abstract

The tripodal amino-phosphinate ligands, tris(4-(phenylphosphinato)-3-benzyl-3-azabutyl) amine (H(3)ppba center dot 2HCl center dot H2O) and tris(4-(phenylphosphinato)-3-azabutyl) amine (H(3)ppa center dot HCl center dot H2O) were synthesized and reacted with Al3+, Ga3+, In3+ and the lanthanides (Ln(3+)). At 2 : 1 H(3)ppba to metal ratios, complexes of the type [M(H(3)ppba)(2)](3+) (M = Al3+, Ga3+, In3+, Ho3+-Lu3+) were isolated. The bicapped [Ga(H(3)ppba)(2)](NO3)(2)Cl center dot 3CH(3)OH was structurally characterized and was shown indirectly by various techniques to be isostructural with the other [M(H(3)ppba)(2)](3+) complexes. Also, at 2:1 H(3)ppba to metal ratios, complexes of the type [M(H(4)ppba)(2)](5+) (M = La3+-Tb3+) were characterized, and the X-ray structure of [Gd(H(4)ppba)(2)](NO3)(4)Cl center dot 3CH(3)OH was determined. At 1:1 H(3)ppba to metal ratios, complexes of the type [M(H(4)ppba)](4+) (M = La3+-Er3+) were isolated and characterized. Elemental analysis and spectroscopic evidence supported the formation of a 1:1 monocapped complex. Reaction of 1:1 ratios of H(3)ppa with Ln(3+) and In3+ yielded complexes of the type [M(H(3)ppa)](3+) (M = La3+-Yb3+) but with Ga3+, complex of the type [Ga(ppa)]center dot 3H(2)O was obtained. Reaction of 1:1 ratios of H(3)ppa with Ln(3+) and In3+ yielded complexes of the type [M(H(3)ppa)](3+) (M = La3+-Yb3+) but with Ga3+ a neutral complex [Ga(ppa)]center dot 3H(2)O was obtained. The formation of an encapsulated 1:1 complex is supported by elemental analysis and spectroscopic evidence.

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