Highly Selective Molybdenum ONO Pincer Complex Initiates the Living Ring-opening Metathesis Polymerization of Strained Alkynes with Exceptionally Low Polydispersity Indices

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2014 Dec 24

PMID 25535767

Citations 9

Authors

Donatela E Bellone

Justin Bours

Elisabeth H Menke

Felix R Fischer

Affiliations

Soon will be listed here.

Abstract

The pseudo-octahedral molybdenum benzylidyne complex [TolC≡Mo(ONO)(OR)]·KOR (R = CCH3(CF3)2) 1, featuring a stabilizing ONO pincer ligand, initiates the controlled living polymerization of strained dibenzocyclooctynes at T > 60 °C to give high molecular weight polymers with exceptionally low polydispersities (PDI ∼ 1.02). Kinetic analyses reveal that the growing polymer chain attached to the propagating catalyst efficiently limits the rate of propagation with respect to the rate of initiation (kp/ki ∼ 10(-3)). The reversible coordination of KOCCH3(CF3)2 to the propagating catalyst prevents undesired chain-termination and -transfer processes. The ring-opening alkyne metathesis polymerization with 1 has all the characteristics of a living polymerization and enables, for the first time, the controlled synthesis of amphiphilic block copolymers via ROAMP.

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References

Arumugam S, Popik V . Sequential "click" - "photo-click" cross-linker for catalyst-free ligation of azide-tagged substrates. J Org Chem. 2014; 79(6):2702-8. PMC: 3985855. DOI: 10.1021/jo500143v. View

Akoka S, Barantin L, Trierweiler M . Concentration Measurement by Proton NMR Using the ERETIC Method. Anal Chem. 2011; 71(13):2554-7. DOI: 10.1021/ac981422i. View

OReilly M, Ghiviriga I, Abboud K, Veige A . A new ONO3- trianionic pincer-type ligand for generating highly nucleophilic metal-carbon multiple bonds. J Am Chem Soc. 2012; 134(27):11185-95. DOI: 10.1021/ja302222s. View

Jewett J, Sletten E, Bertozzi C . Rapid Cu-free click chemistry with readily synthesized biarylazacyclooctynones. J Am Chem Soc. 2010; 132(11):3688-90. PMC: 2840677. DOI: 10.1021/ja100014q. View

Haberlag B, Freytag M, Daniliuc C, Jones P, Tamm M . Efficient metathesis of terminal alkynes. Angew Chem Int Ed Engl. 2012; 51(52):13019-22. DOI: 10.1002/anie.201207772. View

Paley D, Sedbrook D, Decatur J, Fischer F, Steigerwald M, Nuckolls C . Alcohol-promoted ring-opening alkyne metathesis polymerization. Angew Chem Int Ed Engl. 2013; 52(17):4591-4. DOI: 10.1002/anie.201300758. View

Bunz U . Poly(p-phenyleneethynylene)s by alkyne metathesis. Acc Chem Res. 2001; 34(12):998-1010. DOI: 10.1021/ar010092c. View

Haberlag B, Wu X, Brandhorst K, Grunenberg J, Daniliuc C, Jones P . Preparation of imidazolin-2-iminato molybdenum and tungsten benzylidyne complexes: a new pathway to highly active alkyne metathesis catalysts. Chemistry. 2010; 16(29):8868-77. DOI: 10.1002/chem.201000597. View

Schrock R . High oxidation state multiple metal-carbon bonds. Chem Rev. 2002; 102(1):145-79. DOI: 10.1021/cr0103726. View

10.

Beer S, Hrib C, Jones P, Brandhorst K, Grunenberg J, Tamm M . Efficient room-temperature alkyne metathesis with well-defined imidazolin-2-iminato tungsten alkylidyne complexes. Angew Chem Int Ed Engl. 2007; 46(46):8890-4. DOI: 10.1002/anie.200703184. View

11.

Friscourt F, Ledin P, Mbua N, Flanagan-Steet H, Wolfert M, Steet R . Polar dibenzocyclooctynes for selective labeling of extracellular glycoconjugates of living cells. J Am Chem Soc. 2012; 134(11):5381-9. PMC: 3319718. DOI: 10.1021/ja3002666. View

12.

Poloukhtine A, Mbua N, Wolfert M, Boons G, Popik V . Selective labeling of living cells by a photo-triggered click reaction. J Am Chem Soc. 2009; 131(43):15769-76. PMC: 2776736. DOI: 10.1021/ja9054096. View

13.

McQuade D, Pullen A, Swager T . Conjugated polymer-based chemical sensors. Chem Rev. 2001; 100(7):2537-74. DOI: 10.1021/cr9801014. View

14.

OReilly M, Veige A . Trianionic pincer and pincer-type metal complexes and catalysts. Chem Soc Rev. 2014; 43(17):6325-69. DOI: 10.1039/c4cs00111g. View

15.

Miller A, Labinger J, Bercaw J . Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides. Organometallics. 2011; 30(16):4308-4314. PMC: 3167168. DOI: 10.1021/om200364w. View

16.

OReilly M, Ghiviriga I, Abboud K, Veige A . Unusually stable tungstenacyclobutadienes featuring an ONO trianionic pincer-type ligand. Dalton Trans. 2013; 42(10):3326-36. DOI: 10.1039/c2dt32653a. View

17.

Furstner A . Alkyne metathesis on the rise. Angew Chem Int Ed Engl. 2013; 52(10):2794-819. DOI: 10.1002/anie.201204513. View

18.

Schrock R . Alkyne metathesis by molybdenum and tungsten alkylidyne complexes. Chem Commun (Camb). 2013; 49(49):5529-31. DOI: 10.1039/c3cc42609b. View

19.

Fischer F, Nuckolls C . Design of living ring-opening alkyne metathesis. Angew Chem Int Ed Engl. 2010; 49(40):7257-60. DOI: 10.1002/anie.201003549. View

20.

Wu X, Tamm M . Recent advances in the development of alkyne metathesis catalysts. Beilstein J Org Chem. 2011; 7:82-93. PMC: 3029010. DOI: 10.3762/bjoc.7.12. View