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Issue 19, 2013
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Unprecedented reaction of bridged bis(guanidinate) lanthanide complexes: sterically induced deprotonation

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Abstract

Reaction of LnCl3 with a lithium salt of bridged bis(guanidinate) bearing a rigid naphthalene linker [Li2{LH2}2Li2] (LH2 = 1,8-C10H6{NC(NiPr)(NHiPr)}2) (1), which was synthesized by the reaction of 1,8-diaminonaphthalene with 2 equiv. of nBuLi, followed by treatment with 2 equiv. of N,N′-diisopropylcarbodiimide, yielded the chlorides [LnCl{LH2}] (Ln = Yb (2), Y (3)) in good yields. Metathesis reaction of 2 and 3 with NaN(SiMe3)2 did not afford the corresponding amide complexes, but the deprotonation products of [Ln{LH}]2 (LH = 1,8-C10H6{NC(NiPr)(NHiPr)}{NC(NiPr)2}; Ln = Yb (4), Y (5)) were isolated instead. The LH in 4 and 5 both act as a bridging ligand binding to two metals in a μ–η122 fashion, and the re-arrangement of LH occurred during the reaction. The size of the amido group was found to have a great influence on the outcome of the metathesis reaction. Reaction of 2 with bulky NaNH(C6H3iPr2-2,6) afforded 4 as the only product, whereas the same reaction with less bulky LiNH(C6H4Cl-4) and LiNH(C6H4CH3-4) led to the corresponding amides, [Yb{LH2}(NHC6H4Cl-4)]2 (6) and [Yb{LH2}(NHC6H4CH3-4)]2 (7), respectively. The re-arrangement of ligands was also observed in both cases. A possible pathway for the deprotonation of LH2 was discussed. Molecular structures of 1–7 were determined by X-ray single crystal analysis.

Graphical abstract: Unprecedented reaction of bridged bis(guanidinate) lanthanide complexes: sterically induced deprotonation

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Publication details

The article was received on 01 Dec 2012, accepted on 22 Feb 2013 and first published on 22 Feb 2013


Article type: Paper
DOI: 10.1039/C3DT32882A
Dalton Trans., 2013,42, 7009-7018

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    Unprecedented reaction of bridged bis(guanidinate) lanthanide complexes: sterically induced deprotonation

    C. Wang, X. Zhang, M. Xue, Y. Zhang and Q. Shen, Dalton Trans., 2013, 42, 7009
    DOI: 10.1039/C3DT32882A

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