Mechanisms in heterobimetallic reactivity: Experimental and computational insights for catalyst design in small molecule activation and polymer synthesis

Frances N. Singer; Antoine Buchard

doi:10.1002/9781119448877.ch4

Mechanisms in heterobimetallic reactivity: Experimental and computational insights for catalyst design in small molecule activation and polymer synthesis

Frances N. Singer, Antoine Buchard

Chemistry

Research output: Chapter in Book/Report/Conference proceeding › Chapter

Abstract

Summary In this chapter, the authors discuss indiscriminately examples of heterobimetallic complexes which feature metal–metal bonds as well as complexes in which metal sites have been compartmentalized by tailored ligand architecture. The activation of small molecules such as hydrogen, nitrogen, or carbon dioxide is an attractive approach to synthetic chemistry. The authors describe how heterobimetallic catalysts have been developed for polymerization reactions, including for sustainable polymers such as the ring-opening of lactones and the ring-opening copolymerization of epoxides and carbon dioxide. One of the most efficient methods to synthesize polyolefins is via the coordination insertion polymerization using transition metal catalysts. Evidence that the desired heterobimetallic complexes retain their structure and composition under the conditions of catalysis is paramount to confirm any metal cooperativity and validate any mechanistic investigation that will feed into a subsequent catalyst design process. One challenge in heterobimetallic catalysis is confirming any metal cooperative effect and understanding its origin.

Original language	English
Title of host publication	Polar Organometallic Reagents
Editors	Andrew E. H. Wheatley, Masanobu Uchiyama
Publisher	John Wiley & Sons, Ltd
Pages	133-199
Number of pages	67
ISBN (Print)	9781119448877
DOIs	https://doi.org/10.1002/9781119448877.ch4
Publication status	Published - 4 Mar 2022

Keywords

catalyst design process
heterobimetallic catalysis
heterobimetallic complexes
polymerization reactions
small molecules activation
synthetic chemistry

Access to Document

10.1002/9781119448877.ch4

Cite this

@inbook{df24ae9d5d6a418392022005296377e5,

title = "Mechanisms in heterobimetallic reactivity: Experimental and computational insights for catalyst design in small molecule activation and polymer synthesis",

abstract = "Summary In this chapter, the authors discuss indiscriminately examples of heterobimetallic complexes which feature metal–metal bonds as well as complexes in which metal sites have been compartmentalized by tailored ligand architecture. The activation of small molecules such as hydrogen, nitrogen, or carbon dioxide is an attractive approach to synthetic chemistry. The authors describe how heterobimetallic catalysts have been developed for polymerization reactions, including for sustainable polymers such as the ring-opening of lactones and the ring-opening copolymerization of epoxides and carbon dioxide. One of the most efficient methods to synthesize polyolefins is via the coordination insertion polymerization using transition metal catalysts. Evidence that the desired heterobimetallic complexes retain their structure and composition under the conditions of catalysis is paramount to confirm any metal cooperativity and validate any mechanistic investigation that will feed into a subsequent catalyst design process. One challenge in heterobimetallic catalysis is confirming any metal cooperative effect and understanding its origin.",

keywords = "catalyst design process, heterobimetallic catalysis, heterobimetallic complexes, polymerization reactions, small molecules activation, synthetic chemistry",

author = "Singer, {Frances N.} and Antoine Buchard",

year = "2022",

month = mar,

day = "4",

doi = "10.1002/9781119448877.ch4",

language = "English",

isbn = "9781119448877",

pages = "133--199",

editor = "Wheatley, {Andrew E. H.} and Masanobu Uchiyama",

booktitle = "Polar Organometallic Reagents",

publisher = "John Wiley & Sons, Ltd",

}

Mechanisms in heterobimetallic reactivity: Experimental and computational insights for catalyst design in small molecule activation and polymer synthesis. / Singer, Frances N.; Buchard, Antoine.
Polar Organometallic Reagents. ed. / Andrew E. H. Wheatley; Masanobu Uchiyama. John Wiley & Sons, Ltd, 2022. p. 133-199.

Research output: Chapter in Book/Report/Conference proceeding › Chapter

TY - CHAP

T1 - Mechanisms in heterobimetallic reactivity: Experimental and computational insights for catalyst design in small molecule activation and polymer synthesis

AU - Singer, Frances N.

AU - Buchard, Antoine

PY - 2022/3/4

Y1 - 2022/3/4

N2 - Summary In this chapter, the authors discuss indiscriminately examples of heterobimetallic complexes which feature metal–metal bonds as well as complexes in which metal sites have been compartmentalized by tailored ligand architecture. The activation of small molecules such as hydrogen, nitrogen, or carbon dioxide is an attractive approach to synthetic chemistry. The authors describe how heterobimetallic catalysts have been developed for polymerization reactions, including for sustainable polymers such as the ring-opening of lactones and the ring-opening copolymerization of epoxides and carbon dioxide. One of the most efficient methods to synthesize polyolefins is via the coordination insertion polymerization using transition metal catalysts. Evidence that the desired heterobimetallic complexes retain their structure and composition under the conditions of catalysis is paramount to confirm any metal cooperativity and validate any mechanistic investigation that will feed into a subsequent catalyst design process. One challenge in heterobimetallic catalysis is confirming any metal cooperative effect and understanding its origin.

AB - Summary In this chapter, the authors discuss indiscriminately examples of heterobimetallic complexes which feature metal–metal bonds as well as complexes in which metal sites have been compartmentalized by tailored ligand architecture. The activation of small molecules such as hydrogen, nitrogen, or carbon dioxide is an attractive approach to synthetic chemistry. The authors describe how heterobimetallic catalysts have been developed for polymerization reactions, including for sustainable polymers such as the ring-opening of lactones and the ring-opening copolymerization of epoxides and carbon dioxide. One of the most efficient methods to synthesize polyolefins is via the coordination insertion polymerization using transition metal catalysts. Evidence that the desired heterobimetallic complexes retain their structure and composition under the conditions of catalysis is paramount to confirm any metal cooperativity and validate any mechanistic investigation that will feed into a subsequent catalyst design process. One challenge in heterobimetallic catalysis is confirming any metal cooperative effect and understanding its origin.

KW - catalyst design process

KW - heterobimetallic catalysis

KW - heterobimetallic complexes

KW - polymerization reactions

KW - small molecules activation

KW - synthetic chemistry

U2 - 10.1002/9781119448877.ch4

DO - 10.1002/9781119448877.ch4

M3 - Chapter

SN - 9781119448877

SP - 133

EP - 199

BT - Polar Organometallic Reagents

A2 - Wheatley, Andrew E. H.

A2 - Uchiyama, Masanobu

PB - John Wiley & Sons, Ltd

ER -