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Article Dans Une Revue Dalton Transactions Année : 2013

Organometallic strontium borohydrides - synthesis, catalytic studies, and DFT calculations

Résumé

[Ca(BH4)2(THF)2] (1a), a known compound, was easily prepared following a convenient new procedure from [Ca(OMe)2] and BH3*THF in THF. Reaction of 1a with KCp* (Cp* = (η5-C5Me5)) and K{(Me3SiNPPh2)2CH} in a 1 : 1 ratio in THF resulted in the corresponding dimeric heteroleptic mono-borohydride derivatives [Cp*Ca(BH4)(THF)n]2 (2a) and [{(Me3SiNPPh2)2CH}Ca(BH4)(THF)2] (3a), respectively. Both compounds were fully characterized and the solid-state structure of 3a was established by single crystal X-ray diffraction. Compounds 1a, 2a, and 3a, together with the earlier reported compounds [Sr(BH4)2(THF)2] (1b), [Cp*Sr(BH4)(THF)2]2 (2b), and [{(Me3SiNPPh2)2CH}Sr(BH4)(THF)2] (3b), were used as initiators for the ROP of polar monomers. The general performances of the complexes in the ROP of ε-caprolactone and L-lactide demonstrate a relatively good control of the polymerization under the operating conditions established. α,ω-Dihydroxytelechelic poly(ε-caprolactone)s (PCLs) and poly(lactide)s (PLAs) were thus synthesized. DFT calculations on the initiation step of the ROP of ε-CL were carried out. Gibbs free energy profiles were determined for the three calcium complexes highlighting slightly more active calcium complexes as compared to strontium analogues, in agreement with experimental findings.

Domaines

Catalyse
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Dates et versions

hal-00874609 , version 1 (18-10-2013)

Identifiants

Citer

Magdalena Kuzdrowska, Liana Annunziata, Sébastian Marks, Matthias Schmid, Cédric G Jaffredo, et al.. Organometallic strontium borohydrides - synthesis, catalytic studies, and DFT calculations. Dalton Transactions, 2013, 42, pp.9352-9360. ⟨10.1039/C3DT00037K⟩. ⟨hal-00874609⟩
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