N-Heterocyclic Carbene, High Oxidation State Molybdenum Alkylidene Complexes: Functional-Group-Tolerant Cationic Metathesis Catalysts
作者： Michael R. Buchmeiser , Suman Sen , Jörg Unold , Wolfgang Frey
关键词:
摘要: We synthesized the first N-heterocyclic carbene (NHC) complexes of Schrock’s molybdenum imido alkylidene bis(triflate) complexes. Unlike existing complexes, novel 16-electron represent metathesis active, functional-group-tolerant catalysts. Single-crystal X-ray structures two representatives this class Schrock catalysts are presented and reactivity is discussed in view their structural peculiarities. In presence monomer (substrate), these form cationic species can be employed ring-closing (RCM), ring-opening polymerization (ROMP), as well cyclopolymerization α,ω-diynes. Monomers containing functional groups, which not tolerated by variations catalyst, e.g., sec-amine, hydroxy, carboxylic acid moieties, used. These therefore hold great promise both organic polymer chemistry, where they allow for use protic monomers.
sci-hub.se 参考文章(25)
Zachary J. Tonzetich, Annie J. Jiang, Richard R. Schrock, Peter Müller, Cationic imido alkylidene complexes of molybdenum supported by β-diketonate and β-diketiminate ligands Organometallics. ,vol. 25, pp. 4725- 4727 ,(2006) , 10.1021/OM060518X
Eleanor M. Higgins, Jennifer A. Sherwood, Anita G. Lindsay, James Armstrong, Richard S. Massey, Roger W. Alder, AnnMarie C. O'Donoghue, pKas of the conjugate acids of N-heterocyclic carbenes in water Chemical Communications. ,vol. 47, pp. 1559- 1561 ,(2011) , 10.1039/C0CC03367G
A. Scott Gamble, James M. Boncella, Facile synthesis of cationic tungsten(VI) alkylidene complexes Organometallics. ,vol. 12, pp. 2814- 2819 ,(1993) , 10.1021/OM00031A058
Jörg Unold, Dongren Wang, Wolfgang Frey, Michael R. Buchmeiser, Stereo- and regioselective cyclopolymerization of chiral 1,7-octadiynes Polymer Chemistry. ,vol. 4, pp. 4219- 4233 ,(2013) , 10.1039/C3PY00567D
Richard R. Schrock, William E. Crowe, Guillermo C. Bazan, Marcello. DiMare, Marie B. O'Regan, Mark H. Schofield, MONOADDUCTS OF IMIDO ALKYLIDENE COMPLEXES, SYN AND ANTI ROTAMERS, AND ALKYLIDENE LIGAND ROTATION Organometallics. ,vol. 10, pp. 1832- 1843 ,(1991) , 10.1021/OM00052A033
Annie J. Jiang, Jeffrey H. Simpson, Peter Müller, Richard R. Schrock, Fundamental studies of tungsten alkylidene imido monoalkoxidepyrrolide complexes. Journal of the American Chemical Society. ,vol. 131, pp. 7770- 7780 ,(2009) , 10.1021/JA9012694
Michael R. Buchmeiser, Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials. Chemical Reviews. ,vol. 100, pp. 1565- 1604 ,(2000) , 10.1021/CR990248A
Benjamin Autenrieth, Emily Baird Anderson, Dongren Wang, Michael R. Buchmeiser, Reactivity of the Dicationic Ruthenium–Alkylidene Complex [Ru(DMF)3(IMesH2)(=CH—2—(2—PrO)—C6H4)],2+(BF4−)2] in Ring-Opening Metathesis and Cyclopolymerization Macromolecular Chemistry and Physics. ,vol. 214, pp. 33- 40 ,(2013) , 10.1002/MACP.201200544
Scott M. Rocklage, Richard R. Schrock, Melvyn Rowen Churchill, Harvey J. Wasserman, Multiple metal carbon bonds. Part 29. Facile conversion of tungsten(VI) neopentylidyne complexes into oxo and imido neopentylidene complexes and the crystal structure of W(CCMe3)(PHPh)(PEt3)2Cl2 Organometallics. ,vol. 1, pp. 1332- 1338 ,(1982) , 10.1021/OM00070A015
Richard R. Schrock, Jin-Kyu Lee, Richard O'Dell, John H. Oskam, Exploring Factors That Determine Cis/Trans Structure and Tacticity in Polymers Prepared by Ring-Opening Metathesis Polymerizations with Initiators of the Type syn- and anti-Mo(NAr)(CHCMe2Ph)(OR)2. Observation of a Temperature-Dependent Cis/Trans Ratio Macromolecules. ,vol. 28, pp. 5933- 5940 ,(1995) , 10.1021/MA00121A033