Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones

Matthias Westerhausen, Stefan Schneiderbauer, Alexander N. Kneifel, Yvonne Söltl, Peter Mayer, Heinrich Nöth, Zhiyuan Zhong, Pieter J. Dijkstra, Jan Feijen

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Abstract

The equimolar reaction of calcium bis[bis(trimethylsilyl)amide] with 2,2,6,6-tetramethylheptane-3,5-dione (Htmhd) in THF yields liquid mononuclear [Ca(tmhd){N(SiMe3)2}(THF)3] (1). A similar reaction in toluene with a stoichiometric ratio of 2:3 gives the dinuclear complex [{(THF)Ca}2(tmhd)2(µ-tmhd){µ-N(SiMe3)2}] (2). The calcium atoms of these complexes are in a distorted octahedral environment. In 2 the complex consists of two octahedra connected by a common face of one nitrogen base and two oxygen atoms; the bridging Ca-N bond lengths are extremely large. The metalation of the tetradentate Jacobsen reagent with calcium bis[bis(trimethylsilyl)amide] in 1,2-dimethoxyethane (DME) gives the corresponding calcium complex 3, nearly quantitatively, as its DME adduct. The calcium atom is in an unusual trigonal prismatic coordination sphere. The metathesis reaction of 3 with tin(II) chloride yields the corresponding yellow tin(II) complex with the metal atom in a distorted square-pyramidal environment. Complexes 2 and 3 show catalytic reactivity in the ring-opening polymerization of cyclic esters such as lactones and lactides.
Original languageUndefined
Pages (from-to)3432-3439
JournalEuropean journal of inorganic chemistry
Volume18
Issue number18
DOIs
Publication statusPublished - 2003

Keywords

  • TiN
  • Calcium
  • Ring-opening polymerization
  • N ligands
  • O ligands
  • IR-71927
  • METIS-216620

Cite this

Westerhausen, Matthias ; Schneiderbauer, Stefan ; Kneifel, Alexander N. ; Söltl, Yvonne ; Mayer, Peter ; Nöth, Heinrich ; Zhong, Zhiyuan ; Dijkstra, Pieter J. ; Feijen, Jan. / Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones. In: European journal of inorganic chemistry. 2003 ; Vol. 18, No. 18. pp. 3432-3439.
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title = "Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones",
abstract = "The equimolar reaction of calcium bis[bis(trimethylsilyl)amide] with 2,2,6,6-tetramethylheptane-3,5-dione (Htmhd) in THF yields liquid mononuclear [Ca(tmhd){N(SiMe3)2}(THF)3] (1). A similar reaction in toluene with a stoichiometric ratio of 2:3 gives the dinuclear complex [{(THF)Ca}2(tmhd)2(µ-tmhd){µ-N(SiMe3)2}] (2). The calcium atoms of these complexes are in a distorted octahedral environment. In 2 the complex consists of two octahedra connected by a common face of one nitrogen base and two oxygen atoms; the bridging Ca-N bond lengths are extremely large. The metalation of the tetradentate Jacobsen reagent with calcium bis[bis(trimethylsilyl)amide] in 1,2-dimethoxyethane (DME) gives the corresponding calcium complex 3, nearly quantitatively, as its DME adduct. The calcium atom is in an unusual trigonal prismatic coordination sphere. The metathesis reaction of 3 with tin(II) chloride yields the corresponding yellow tin(II) complex with the metal atom in a distorted square-pyramidal environment. Complexes 2 and 3 show catalytic reactivity in the ring-opening polymerization of cyclic esters such as lactones and lactides.",
keywords = "TiN, Calcium, Ring-opening polymerization, N ligands, O ligands, IR-71927, METIS-216620",
author = "Matthias Westerhausen and Stefan Schneiderbauer and Kneifel, {Alexander N.} and Yvonne S{\"o}ltl and Peter Mayer and Heinrich N{\"o}th and Zhiyuan Zhong and Dijkstra, {Pieter J.} and Jan Feijen",
year = "2003",
doi = "10.1002/ejic.200300286",
language = "Undefined",
volume = "18",
pages = "3432--3439",
journal = "European journal of inorganic chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag",
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Westerhausen, M, Schneiderbauer, S, Kneifel, AN, Söltl, Y, Mayer, P, Nöth, H, Zhong, Z, Dijkstra, PJ & Feijen, J 2003, 'Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones' European journal of inorganic chemistry, vol. 18, no. 18, pp. 3432-3439. https://doi.org/10.1002/ejic.200300286

Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones. / Westerhausen, Matthias; Schneiderbauer, Stefan; Kneifel, Alexander N.; Söltl, Yvonne; Mayer, Peter; Nöth, Heinrich; Zhong, Zhiyuan; Dijkstra, Pieter J.; Feijen, Jan.

In: European journal of inorganic chemistry, Vol. 18, No. 18, 2003, p. 3432-3439.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Organocalcium compounds with catalytic activity for the ring-opening polymerization of lactones

AU - Westerhausen, Matthias

AU - Schneiderbauer, Stefan

AU - Kneifel, Alexander N.

AU - Söltl, Yvonne

AU - Mayer, Peter

AU - Nöth, Heinrich

AU - Zhong, Zhiyuan

AU - Dijkstra, Pieter J.

AU - Feijen, Jan

PY - 2003

Y1 - 2003

N2 - The equimolar reaction of calcium bis[bis(trimethylsilyl)amide] with 2,2,6,6-tetramethylheptane-3,5-dione (Htmhd) in THF yields liquid mononuclear [Ca(tmhd){N(SiMe3)2}(THF)3] (1). A similar reaction in toluene with a stoichiometric ratio of 2:3 gives the dinuclear complex [{(THF)Ca}2(tmhd)2(µ-tmhd){µ-N(SiMe3)2}] (2). The calcium atoms of these complexes are in a distorted octahedral environment. In 2 the complex consists of two octahedra connected by a common face of one nitrogen base and two oxygen atoms; the bridging Ca-N bond lengths are extremely large. The metalation of the tetradentate Jacobsen reagent with calcium bis[bis(trimethylsilyl)amide] in 1,2-dimethoxyethane (DME) gives the corresponding calcium complex 3, nearly quantitatively, as its DME adduct. The calcium atom is in an unusual trigonal prismatic coordination sphere. The metathesis reaction of 3 with tin(II) chloride yields the corresponding yellow tin(II) complex with the metal atom in a distorted square-pyramidal environment. Complexes 2 and 3 show catalytic reactivity in the ring-opening polymerization of cyclic esters such as lactones and lactides.

AB - The equimolar reaction of calcium bis[bis(trimethylsilyl)amide] with 2,2,6,6-tetramethylheptane-3,5-dione (Htmhd) in THF yields liquid mononuclear [Ca(tmhd){N(SiMe3)2}(THF)3] (1). A similar reaction in toluene with a stoichiometric ratio of 2:3 gives the dinuclear complex [{(THF)Ca}2(tmhd)2(µ-tmhd){µ-N(SiMe3)2}] (2). The calcium atoms of these complexes are in a distorted octahedral environment. In 2 the complex consists of two octahedra connected by a common face of one nitrogen base and two oxygen atoms; the bridging Ca-N bond lengths are extremely large. The metalation of the tetradentate Jacobsen reagent with calcium bis[bis(trimethylsilyl)amide] in 1,2-dimethoxyethane (DME) gives the corresponding calcium complex 3, nearly quantitatively, as its DME adduct. The calcium atom is in an unusual trigonal prismatic coordination sphere. The metathesis reaction of 3 with tin(II) chloride yields the corresponding yellow tin(II) complex with the metal atom in a distorted square-pyramidal environment. Complexes 2 and 3 show catalytic reactivity in the ring-opening polymerization of cyclic esters such as lactones and lactides.

KW - TiN

KW - Calcium

KW - Ring-opening polymerization

KW - N ligands

KW - O ligands

KW - IR-71927

KW - METIS-216620

U2 - 10.1002/ejic.200300286

DO - 10.1002/ejic.200300286

M3 - Article

VL - 18

SP - 3432

EP - 3439

JO - European journal of inorganic chemistry

JF - European journal of inorganic chemistry

SN - 1434-1948

IS - 18

ER -