Rational approach to polymer-supported catalysts: Synergy between catalytic reaction mechanism and polymer design

Nandita Madhavan, Christopher W. Jones, Marcus Weck

Research output: Contribution to journalArticle

Abstract

Supported catalysis is emerging as a cornerstone of transition metal catalysis, as environmental awareness necessitates "green" methodologies and transition metal resources become scarcer and more expensive. Although these supported systems are quite useful, especially in their capacity for transition metal catalyst recycling and recovery, higher activity and selectivity have been elusive compared with nonsupported catalysts. This Account describes recent developments in polymer-supported metal-salen complexes, which often surpass nonsupported analogues in catalytic activity and selectivity, demonstrating the effectiveness of a systematic, logical approach to designing supported catalysts from a detailed understanding of the catalytic reaction mechanism. Over the past few decades, a large number of transition metal complex catalysts have been supported on a variety of materials ranging from polymers to mesoporous silica. In particular, soluble polymer supports are advantageous because of the development of controlled and living polymerization methods that are tolerant to a wide variety of functional groups, including controlled radical polymerizations and ring-opening metathesis polymerization. These methods allow for tuning the density and structure of the catalyst sites along the polymer chain, thereby enabling the development of structure-property relationships between a catalyst and its polymer support. The fine-tuning of the catalyst-support interface, in combination with a detailed understanding of catalytic reaction mechanisms, not only permits the generation of reusable and recyclable polymer-supported catalysts but also facilitates the design and realization of supported catalysts that are significantly more active and selective than their nonsupported counterparts. These superior supported catalysts are accessible through the optimization of four basic variables in their design: (i) polymer backbone rigidity, (ii) the nature of the linker, (iii) catalyst site density, and (iv) the nature of the catalyst attachment. Herein, we desaibe the design of polymer supports tuned to enhance the catalytic activity or decrease, or even eliminate, decomposition pathways of salen-based transition metal catalysts that follow either a monometallic or a bimetallic reaction mechanism. These findings result in the creation of some of the most active and selective salen catalysts in the literature.

Original languageEnglish (US)
Pages (from-to)1153-1165
Number of pages13
JournalAccounts of Chemical Research
Volume41
Issue number9
DOIs
StatePublished - Sep 2008

Fingerprint

Catalyst supports
Polymers
Catalysts
Transition metals
Catalyst activity
Catalyst selectivity
Catalysis
Tuning
Living polymerization
Coordination Complexes
Ring opening polymerization
Free radical polymerization
Metal complexes
Silicon Dioxide
Rigidity
Functional groups
Recycling
Decomposition
Recovery

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Rational approach to polymer-supported catalysts : Synergy between catalytic reaction mechanism and polymer design. / Madhavan, Nandita; Jones, Christopher W.; Weck, Marcus.

In: Accounts of Chemical Research, Vol. 41, No. 9, 09.2008, p. 1153-1165.

Research output: Contribution to journalArticle

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