Alkaline-Earth Metal Complexes in Homogeneous Polymerization Catalysis

Carpentier, Jean‐François; Sarazin, Yann

doi:10.1007/978-3-642-36270-5_5

Cited by 38 publications

(28 citation statements)

References 120 publications

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“…About 8 years ago, we initiated a research program in our laboratory aimed at better understanding the coordination and organometallic chemistry of the large alkaline earths, and at implementing Ae catalysts in ring‐opening polymerizations23,29 and other reactions for the production of fine chemicals. We are presenting here an account of the key results obtained in our group on the design and performance of Ae precatalysts for the atom‐efficient creation of CN, CP, and SiN bonds.…”

Section: Introductionmentioning

confidence: 99%

Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis

Sarazin

Carpentier

2016

The Chemical Record

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The large alkaline earths (Ae), calcium, strontium and barium, have in the past 15 years yielded a brand new generation of heteroleptic molecular catalysts for the production of fine chemicals. However, the integrity of these complexes is often plagued by ligand redistribution equilibria in solution. This personal account retraces the paths followed in our research group towards the design of stable heteroleptic alkalino-earth complexes, including the use of intramolecular noncovalent Ae···H-Si and Ae···F-C interactions. Their implementation as homogenous precatalysts for reactions such as the intramolecular and intermolecular hydroamination and hydrophosphination of activated alkenes, the hydrophosphonylation of ketones, and the dehydrogenative coupling of amines and hydrosilanes that enable the efficient and controlled formations of CP, CN, or SiN σ-bonds, is presented in a synthetic perspective that highlights their overall outstanding catalytic performance.

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Section: Introductionmentioning

confidence: 99%

Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis

Sarazin

Carpentier

2016

The Chemical Record

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“… 15 Additionally, the use of calcium compounds in homogeneous catalysis has received increasing attention, with applications in polymerization catalysis, hydroamination, and hydrosilylation. 16 − 20 The earth abundance of calcium, as well as its biocompatibility, provides motivation for further development of Ca-based catalysts.…”

Section: Introductionmentioning

confidence: 99%

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

et al. 2014

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Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.

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“…Commercial polyester materials are currently produced by polycondensation reactions between diols and diacids at high reaction temperature and prolonged reaction times to afford high-molecular weight polyesters [1,2]. In recent years, a broad range of biodegradable polyesters have been obtained via ring-opening polymerization (ROP) of cyclic esters (Scheme 1a) as a more sustainable alternative to traditional polyester materials [3][4][5][6][7][8][9][10]. In fact, polycaprolactone and polylactide have already been used for several applications [11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

et al. 2021

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The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

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Alkaline-Earth Metal Complexes in Homogeneous Polymerization Catalysis

Cited by 38 publications

References 120 publications

Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis

Calcium, Strontium and Barium Homogeneous Catalysts for Fine Chemicals Synthesis

Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

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