These tools will no longer be maintained as of December 31, 2024. Archived website can be found here. PubMed4Hh GitHub repository can be found here. Contact NLM Customer Service if you have questions.
Pubmed for Handhelds
PUBMED FOR HANDHELDS
Search MEDLINE/PubMed
Title: Mononuclear, five-coordinate lanthanide amido and aryloxide complexes bearing tetradentate (N2O2) Schiff bases. Author: Schuetz SA, Silvernail CM, Incarvito CD, Rheingold AL, Clark JL, Day VW, Belot JA. Journal: Inorg Chem; 2004 Oct 04; 43(20):6203-14. PubMed ID: 15446865. Abstract: Two monomeric, five-coordinate lanthanide complexes, [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[2,6-bis(tert-butyl)-4-methylphenoxide] and [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide], were isolated from the reactions of 2,6-bis(tert-butyl)-4-methylphenol with [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]lanthanide[bis(trimethylsilyl)amido] (lanthanide = Er(3+) and Sm(3+)). The purified phenoxides were recovered in excellent yields and analytical purity, and the reactions proceeded cleanly without Schiff-base degradation or cluster formation. Analogously, [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[bis(trimethylsilyl)amido] was also directly converted to [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide]; however, a less sterically demanding alcohol (i.e., ethanol) yielded a neutral trinuclear oxo alkoxide species with each dianionic Schiff base asymmetrically bridging through micro-oxo interactions. In this polynuclear cluster, each symmetry-related, seven-coordinate erbium(III) ion exhibits monocapped trigonal prismatic geometry, which assembles by sharing triangular capped faces. Single-crystal X-ray diffraction revealed square-pyramidal metal coordination in each five-coordinate lanthanide ion with varied S(4) ruffling of the "square base" donor atoms and the six-membered propylene diamine chelate ring adopting the boat conformation. To contrast the effect of subtle ligand changes, we also report the synthesis and characterization of [bis-5,5'-(2,2-dimethyl-1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[bis(trimethylsilyl)amido], having gem-dimethyl substituents appended to the propylene bridge central carbon. The six-membered diamine chelate ring in this compound adopts the chair conformation without metal-hydrocarbon interaction. Also presented are qualitative activity observations and polymerization data for the polymerization of rac-lactide and epsilon-caprolactone using the five-coordinate lanthanide amidos and phenoxides.[Abstract] [Full Text] [Related] [New Search]