Chiral alkaline earth metal complexes with M-Se direct bond (M = Mg, Ca, Sr, Ba): Syntheses, structures and ε-caprolactone polymerisation

Kottalanka, R K and Adimulam, H and Panda, Tarun K (2015) Chiral alkaline earth metal complexes with M-Se direct bond (M = Mg, Ca, Sr, Ba): Syntheses, structures and ε-caprolactone polymerisation. RSC Advances, 47 (5). pp. 37755-37767. ISSN 2046-2069

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Abstract

We report here a series of enantiomeric pure alkaline earth metal complexes, each with a metallic direct bond of selenium, with {HN(R-∗CHMePh)(P(Se)Ph2)} (1a) and {HN(S-∗CHMePh)(P(Se)Ph2)} (1b), synthesised using two routes. The first route involves a trans metalation reaction of enantiomeric pure potassium phosphinoselenoic amide [K{N(R-∗CHMePh)(Ph2P(Se))}{THF}n] (2a) or [K{N(S-∗CHMePh)(Ph2P(Se))}{THF}n] (2b) prepared from the reaction between either 1a or 1b and [KN(SiMe3)2], and the corresponding alkaline earth metal diiodies in THF at room temperature to afford the enantiomeric pure complexes of composition [M{N(R-∗CHMePh)P(Se)Ph2}2(THF)n] [M = Mg (3a), n = 1; M = Ca (4a), Sr (5a) and Ba (6a), n = 2] and [M{N(S-∗CHMePh)P(Se)Ph2}2(THF)n] [M = Mg (3b), n = 1; M = Ca (4b), Sr (5b) and Ba (6b), n = 2]. The same heavier alkaline earth metal complexes (4a-6a and 4b-6b) can also be obtained through the silylamine elimination method using the corresponding metal bis(trimethylsilyl)amides [M{N(SiMe3)2}2(THF)n] (M = Ca, Sr, Ba) with phosphinoselenoic amine ligands 1a and 1b in ambient conditions. The solid-state structures of the metal complexes 4a-6a and 4b-6b were established using single-crystal X-ray diffraction analysis. In the solid state, all the metal complexes crystallise in the monoclinic P21 space group and each phosphinoselenoic amido ligand is ligated to the metal ion in a bidentate fashion. We also report the syntheses and structures of chiral amidophosphine-borane ligands {HN(R-∗CHMePh)(P(BH3)Ph2)} (7a) and {HN(S-∗CHMePh)(P(BH3)Ph2)} (7b) and the corresponding homoleptic barium complexes of composition [Ba{N(R-∗CHMePh)P(BH3)Ph2}2(THF)2] (8a) and [Ba{N(R-∗CHMePh)P(BH3)Ph2}2(THF)2] (8b). The molecular structures of 8a and 8b in the solid state confirm the attachment of chiral amidophosphine-borane ligands to the barium ions. The complexes 5 and 6 were tested as catalysts for the ring-opening polymerisation of ε-caprolactone. High activity in relation to the barium complexes 6a and 6b is observed, with moderate to narrow polydispersity index.

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IITH Creators:
IITH CreatorsORCiD
Panda, Tarun Khttp://orcid.org/0000-0003-0975-0118
Item Type: Article
Additional Information: We thank Prof. K. Mashima, Division of Chemistry, Graduate School of Engi- neering Science, Osaka University for providing the facility to measure the polymers.
Uncontrolled Keywords: Alkaline earth metals; Alkalinity; Amides; Calcium; Enantiomers; Ligands; Metal complexes; Metal ions; Metals; Polymerization; Single crystals; Synthesis (chemical); X ray diffraction analysis Ambient conditions; Elimination method; Metalation reaction; Polydispersity indices; Room temperature; Single crystal X-ray diffraction analysis; Solid-state structures; Trimethylsilyl
Subjects: Chemistry
Divisions: Department of Chemistry
Depositing User: Team Library
Date Deposited: 18 May 2015 06:54
Last Modified: 07 Sep 2017 10:54
URI: http://raiithold.iith.ac.in/id/eprint/1509
Publisher URL: https://doi.org/10.1039/c5ra04495b
OA policy: http://www.sherpa.ac.uk/romeo/issn/2046-2069/
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