Issue 47, 2009
From the journal:

Dalton Transactions

1,1,3,3-Tetramethylguanidine solvated lanthanide aryloxides: pre-catalysts for intramolecular hydroalkoxylation†

Thomas E. Janini,b   Robert Rakosi III,a   Christopher B. Durr,a   Jeffrey A. Bertkea  and  Scott D. Bunge*a  

* Corresponding authors

a Department of Chemistry, Kent State University, Kent, OH, USA
E-mail: sbunge@kent.edu
Fax: +1 330 6723816
Tel: +1 330 6729445

b Agricultural Technical Institute, The Ohio State University, Wooster, OH, USA
E-mail: janini.4@osu.edu
Fax: +1 330 2871333
Tel: +1 330 2871287

Abstract

The synthesis and structural characterization of six 1,1,3,3-tetramethylguanidine (H-TMG) solvated lanthanide aryloxide complexes are reported. Ln[N{Si(CH3)3}2]3 (Ln = Nd, La) was reacted with two equivalents of both H-TMG and HOAr {HOAr = HOC6H2(CMe3)2-2,6 (H-DBP) or HOC6H2(CMe3)2-2,6-CH3-4 (H-4MeDBP)} and one equivelent of ethanol (HOEt) to yield the corresponding [Nd(H-TMG)2(4MeDBP)2(OEt)] (1) and [La(H-TMG)2(DBP)2(OEt)] (2). Compounds 1 and 2 were further reacted with 4-pentyn-1-ol {HO(CH2)3C[triple bond, length as m-dash]CH} to isolate [Nd(H-TMG)2(4MeDBP)2{O(CH2)3C[triple bond, length as m-dash]CH}] (3) and [La(H-TMG)2(DBP)2{O(CH2)3C[triple bond, length as m-dash]CH}] (4), respectively. Three equivalents of HOAr and one equivalent of H-TMG were additionally reacted with Ln[N{Si(CH3)3}2]3 to generate [Nd(4MeDBP)3(H-TMG)] (5) and [La(DBP)3(H-TMG)] (6). In order to examine the formation of 1–6, the interaction of H-TMG and HOAr was further examined in solution and the hydrogen bonded complexes (H-TMG:HOAr), 7 and 8, were isolated. Upon successful isolation of 1–6, the utility of 1, 2, 4 and 5 as pre-catalysts for the intramolecular hydroalkoxylation of 4-pentyn-1-ol was investigated. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and 1H and 13C NMR investigations.

Graphical abstract: 1,1,3,3-Tetramethylguanidine solvated lanthanide aryloxides: pre-catalysts for intramolecular hydroalkoxylation

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Article information

DOI
https://doi.org/10.1039/B917377C
Article type
Paper
Submitted
24 Aug 2009
Accepted
21 Sep 2009
First published
23 Oct 2009

Dalton Trans., 2009, 10601-10608

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1,1,3,3-Tetramethylguanidine solvated lanthanide aryloxides: pre-catalysts for intramolecular hydroalkoxylation

T. E. Janini, R. Rakosi III, C. B. Durr, J. A. Bertke and S. D. Bunge, Dalton Trans., 2009, 10601 DOI: 10.1039/B917377C

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