Lactide cyclopolymerization kinetics, X-ray structure, and solution dynamics of (tBu-SalAmEE)Al and a cautionary tale of polymetalate formation

Solomon H. Reisberg; Harry J. Hurley; Robert T. Mathers; Joseph M. Tanski; Yutan D.Y.L. Getzler

doi:10.1021/ma400046x

Lactide cyclopolymerization kinetics, X-ray structure, and solution dynamics of (^tBu-SalAmEE)Al and a cautionary tale of polymetalate formation

Solomon H. Reisberg, Harry J. Hurley, Robert T. Mathers, Joseph M. Tanski, Yutan D.Y.L. Getzler

Penn State New Kensington

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

The complex (^tBu-SalAmEE)Al (^tBu-SalAmEEH₃ = N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-2-(2-aminoethoxy)ethanol, 1) catalyzes the ring-expansion polymerization of lactide to form cyclic poly(lactide) (cPLA). The X-ray structure of 1 was determined, its polymerization kinetics were examined and its interactions with Lewis bases were observed. The data from these experiments are consistent with a coordination-insertion mechanism whose rate-determining step is catalyst rearrangement by loss of a hemilabile, datively bound, bridging ligand ether. cPLA was examined by thermogravimetric analysis and found more stable than its linear counterpart. In the course of these studies, we unexpectedly observed the formation of polymetalate (AlMe(^tBu-SalAmEE)AlMe₂) ₂ (6), which was characterized (X-ray, EA, and ¹H and ¹³C NMR).

Original language	English (US)
Pages (from-to)	3273-3279
Number of pages	7
Journal	Macromolecules
Volume	46
Issue number	9
DOIs	https://doi.org/10.1021/ma400046x
State	Published - May 14 2013

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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@article{23ce2e2a133f4c9dac5c0dba3818d27a,

title = "Lactide cyclopolymerization kinetics, X-ray structure, and solution dynamics of (tBu-SalAmEE)Al and a cautionary tale of polymetalate formation",

abstract = "The complex (tBu-SalAmEE)Al (tBu-SalAmEEH3 = N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-2-(2-aminoethoxy)ethanol, 1) catalyzes the ring-expansion polymerization of lactide to form cyclic poly(lactide) (cPLA). The X-ray structure of 1 was determined, its polymerization kinetics were examined and its interactions with Lewis bases were observed. The data from these experiments are consistent with a coordination-insertion mechanism whose rate-determining step is catalyst rearrangement by loss of a hemilabile, datively bound, bridging ligand ether. cPLA was examined by thermogravimetric analysis and found more stable than its linear counterpart. In the course of these studies, we unexpectedly observed the formation of polymetalate (AlMe(tBu-SalAmEE)AlMe2) 2 (6), which was characterized (X-ray, EA, and 1H and 13C NMR).",

author = "Reisberg, {Solomon H.} and Hurley, {Harry J.} and Mathers, {Robert T.} and Tanski, {Joseph M.} and Getzler, {Yutan D.Y.L.}",

year = "2013",

month = may,

day = "14",

doi = "10.1021/ma400046x",

language = "English (US)",

volume = "46",

pages = "3273--3279",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "9",

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TY - JOUR

T1 - Lactide cyclopolymerization kinetics, X-ray structure, and solution dynamics of (tBu-SalAmEE)Al and a cautionary tale of polymetalate formation

AU - Reisberg, Solomon H.

AU - Hurley, Harry J.

AU - Mathers, Robert T.

AU - Tanski, Joseph M.

AU - Getzler, Yutan D.Y.L.

PY - 2013/5/14

Y1 - 2013/5/14

N2 - The complex (tBu-SalAmEE)Al (tBu-SalAmEEH3 = N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-2-(2-aminoethoxy)ethanol, 1) catalyzes the ring-expansion polymerization of lactide to form cyclic poly(lactide) (cPLA). The X-ray structure of 1 was determined, its polymerization kinetics were examined and its interactions with Lewis bases were observed. The data from these experiments are consistent with a coordination-insertion mechanism whose rate-determining step is catalyst rearrangement by loss of a hemilabile, datively bound, bridging ligand ether. cPLA was examined by thermogravimetric analysis and found more stable than its linear counterpart. In the course of these studies, we unexpectedly observed the formation of polymetalate (AlMe(tBu-SalAmEE)AlMe2) 2 (6), which was characterized (X-ray, EA, and 1H and 13C NMR).

AB - The complex (tBu-SalAmEE)Al (tBu-SalAmEEH3 = N,N-bis(3,5-di-tert-butyl-2-hydroxybenzyl)-2-(2-aminoethoxy)ethanol, 1) catalyzes the ring-expansion polymerization of lactide to form cyclic poly(lactide) (cPLA). The X-ray structure of 1 was determined, its polymerization kinetics were examined and its interactions with Lewis bases were observed. The data from these experiments are consistent with a coordination-insertion mechanism whose rate-determining step is catalyst rearrangement by loss of a hemilabile, datively bound, bridging ligand ether. cPLA was examined by thermogravimetric analysis and found more stable than its linear counterpart. In the course of these studies, we unexpectedly observed the formation of polymetalate (AlMe(tBu-SalAmEE)AlMe2) 2 (6), which was characterized (X-ray, EA, and 1H and 13C NMR).

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DO - 10.1021/ma400046x

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JO - Macromolecules

JF - Macromolecules

IS - 9

ER -

Lactide cyclopolymerization kinetics, X-ray structure, and solution dynamics of (^tBu-SalAmEE)Al and a cautionary tale of polymetalate formation

Abstract

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