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| verifiedrevid = 404730935 |
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| Name = 1st Generation Grubbs' Catalyst |
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| verifiedrevid = 447372032 |
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| ImageFile = Grubbs Catalyst 1st Generation.svg |
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| Name = Zhan Catalyst-1B |
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| ImageFile1 = Grubbs-1G-3D-balls.png |
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| ImageFile = Zhan-1b.jpg |
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| IUPACName = |
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| IUPACName = Dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)((5-((dimethylamino)sulfonyl)-2-(1-methylethoxy-O)phenyl)methylene-C)ruthenium(II) |
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| OtherNames = |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = 172222-30-9 |
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| PubChem = |
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| CASNo = 918870-76-5 |
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| ChemSpiderID = 24723209 |
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| SMILES = }} |
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| PubChem = 59856477 |
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| Section2 = {{Chembox Properties |
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| SMILES = Cl2(Cl)(C0N(-c1c(C)cc(C)cc1C)CCN0c1c(C)cc(C)cc1C)=Cc1cc(S(=O)(=O)N(C)C)ccc12C(C)C |
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| C=43|H=72|Cl=2|P=2|Ru=1 |
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| StdInChI=1S/C21H26N2.C12H17NO3S.2ClH.Ru/c1-14-9-16(3)20(17(4)10-14)22-7-8-23(13-22)21-18(5)11-15(2)12-19(21)6;1-9(2)16-12-7-6-11(8-10(12)3)17(14,15)13(4)5;;;/h9-12H,7-8H2,1-6H3;3,6-9H,1-2,4-5H3;2*1H;/q;;;;+2/p-2 |
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| MolarMass = |
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| StdInChIKey = OXLURKCRXVAJQS-UHFFFAOYSA-L |
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| Appearance = Purple solid |
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|Section2={{Chembox Properties |
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| C=33 | H=43 | Cl=2 | N=3 | O=3 | Ru=1 | S=1 |
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| MolarMass = 733.75 g·mol<sup>−1</sup> |
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| Appearance = Green solid |
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| Density = |
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| MeltingPtC = 153 |
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| Section3 = {{Chembox Hazards |
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| MainHazards = |
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| Name = 2nd Generation Grubbs' Catalyst |
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| Name = Zhan Catalyst-1C |
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| ImageFile = Grubbs Catalyst 2nd Generation.png |
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| ImageFile = Zhan-1c.jpg |
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| ImageFile1 = Grubbs-2G-3D-balls.png |
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| ImageFile1 = |
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| IUPACName = Dichloro((5-((dimethylamino)sulfonyl)-2-(1-methylethoxy-O)phenyl)methylene-C)(tricyclohexylphosphine)ruthenium(IV) |
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| Section1 = {{Chembox Identifiers |
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|Section1={{Chembox Identifiers |
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| CASNo = 246047-72-3 |
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| CASNo = 918871-44-0 |
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| ChemSpiderID = 24723353 |
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| SMILES = }} |
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| PubChem = 117065271 |
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| SMILES = Cl2(Cl)((C1CCCCC1)(C1CCCCC1)C1CCCCC1)=Cc1cc(S(=O)(=O)N(C)C)ccc12C(C)C |
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| Section2 = {{Chembox Properties |
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| StdInChI=1S/C18H33P.C12H17NO3S.2ClH.Ru/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-9(2)16-12-7-6-11(8-10(12)3)17(14,15)13(4)5;;;/h16-18H,1-15H2;3,6-9H,1-2,4-5H3;2*1H;/q;;;;+2/p-2 |
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| C=46|H=65|Cl=2|N=2|P=1|Ru=1 |
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| StdInChIKey = GQGVRAHMQZBHRC-UHFFFAOYSA-L |
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| Appearance = Pinkish brown solid |
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|Section2={{Chembox Properties |
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| C=30 | H=50 | Cl=2 | N=1 | O=3 | P=1 | Ru=1 | S=1 |
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| MolarMass = 707.74 g·mol<sup>−1</sup> |
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| Appearance = Brown solid |
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| MeltingPt = 143.5-148.5 °C |
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| MeltingPtC = 145 to 155 |
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A '''Zhan catalyst''' is a type of ]-based organometallic complex used in ]. This class of chemicals is named after the chemist who first synthesized them, Zheng-Yun J. Zhan.<ref name="zhan">{{cite web|last=Zhan|first=Zheng-Yun|title=Recyclable ruthenium catalysts for metathesis reactions |url=https://patents.google.com/patent/US20070043180|work=United States Patent and Trademark Office|access-date=20 April 2017}}</ref> |
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'''Grubbs' Catalyst''' is a ] named after ], the chemist who first synthesized it. There are two generations of the ], as shown on the right.<ref name=grubbs>Grubbs, R.H. ; Wiley-VCH, Germany, '''2003'''.</ref><ref name=grubbs2>Grubbs, R.H.; Trnka, T.M.: in "Ruthenium in Organic Synthesis" (S.-I. Murahashi, Ed.), Wiley-VCH, Germany, '''2004'''.</ref> In contrast to other ] catalysts, Grubbs' Catalysts tolerate other ] in the ] and are compatible with a wide range of solvents.<ref name=vougioukalakis>{{cite journal |last=Vougioukalakis |first=G. C. |coauthors=] |year=2010 |title=Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts |journal=] |pmid=20000700 |volume=110 |issue=3 |pages=1746–1787 |doi=10.1021/cr9002424 }} |
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</ref><ref name=trnka>{{cite journal|title=The Development of L<sub>2</sub>X<sub>2</sub>Ru=CHR Olefin Metathesis Catalysts: An Organometallic Success Story| author= Trnka, T. M.; Grubbs, R. H. |journal= ]| year=2001| volume=34| issue=1| pages= 18–29 | doi=10.1021/ar000114f | pmid=11170353}}</ref> For these reasons, Grubbs' Catalysts are extraordinarily versatile. |
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These catalysts are ruthenium complexes with functionally substituted alkoxybenzylidene carbene ligands, which can be chemically bonded to the surface of resins, PEG chains, and polymers. Like the structurally similar ], they contain an isopropoxystyrene moiety, but include an extra electron-withdrawing sulfonamide group attached to the carbon ''para'' to the phenol oxygen. Of the three catalysts, Zhan Catalyst-1B and -1C both contain a dimethylsulfonamide moiety attached to the aryl ring, while Zhan Catalyst-II is connected to a resin via a sulfonamide linker.<ref>{{cite web|title=Zhan Catalyst-1B |url=https://www.strem.com/catalog/v/44-0082/59/ruthenium_918870-76-5|work=Strem Chemicals Product Catalog|access-date=20 April 2017}}</ref><ref>{{cite web|title=Zhan Catalyst-1C|url=https://www.strem.com/catalog/v/44-0078/59/ruthenium_918871-44-0|work=Strem Chemicals Product Catalog|access-date=20 April 2017}}</ref><ref>{{cite web|title=Zhan Catalyst-II|url=https://www.strem.com/catalog/v/44-0083/59/ruthenium|work=Strem Chemicals Product Catalog|access-date=20 April 2017}}</ref> |
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== First generation catalyst== |
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The First Generation Catalyst is often used in ] to achieve ] (see below), ] (ROMP), acyclic diene metathesis polymerization (ADMET), and ]. It is easily synthesized from RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub>,<ref name=scholl>{{cite journal|title=Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene Ligands|author=Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. |journal=] |year=1999| volume=1 |issue=6| pages=953–956| doi=10.1021/ol990909q}}</ref> ], and ] in a ].<ref name=schwab>{{cite journal| title=Synthesis and Applications of RuCl<sub>2</sub>(=CHR')(PR<sub>3</sub>)<sub>2</sub>: The Influence of the Alkylidene Moiety on Metathesis Activity | author=Schwab, P.; Grubbs, R. H.; Ziller, J. W. |journal=]| year=1996 |volume=118 |issue=1| pages=100–110| doi=10.1021/ja952676d}}</ref> Grubbs' Catalyst is a relatively stable compound in air, which makes handling very easy. The ] name of the 1<sup>st</sup> Generation Catalyst is benzylidene-bis(tricyclohexylphosphine)dichlororuthenium. |
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== History == |
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] is a reaction between two molecules containing double bonds. The groups bonded to the carbon atoms of the double bond are exchanged between molecules, to produce two new molecules containing double bonds with swapped groups. Whether a ] or ] is formed in this type of reaction is determined by the orientation the molecules assume when they coordinate to the catalyst, as well as the ] of the ]s on the double bond of the newly forming molecule. Other catalysts are effective for this reaction, notably those developed by ] (]). |
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The Zhan catalysts were inspired by previous work in the olefin metathesis field. ] first reported the first and second generation of Ru catalysts in 1992, with good metathesis activity. However, the catalysts containing the tricyclohexylphospine ligand were unstable to air and water, and the catalytic activity is not good enough for some multiple substituted olefin substrates.<ref name=nguyen>{{cite journal |last1=Nguyen |first1=S. T. |last2=Johnson|first2= L. K. |last3=Grubbs|first3=R. H. |last4=Ziller|first4=J. W.|year=1992 |title=Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media |journal=] |volume=114 |issue=10 |pages=3974–3975 |doi=10.1021/ja00036a053 |url=https://authors.library.caltech.edu/88217/2/ja00036a053_si_001.pdf }} |
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</ref><ref name=scholl>{{cite journal |last1=Scholl |first1=M. |last2=Ding|first2= S. |last3=Lee|first3=C. W. |last4=Grubbs|first4=R. H.|year=1999 |title=Synthesis and activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene Ligands |journal=] |volume=1 |issue=6 |pages=953–956 |doi=10.1021/ol990909q |pmid=10823227 }} |
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</ref><ref>{{cite web|last=Grubbs|first=Robert H.|title=High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof |url=https://patents.google.com/patent/WO1996004289A1/en|work=World Intellectual Property Organization|access-date=20 April 2017|author2=Sonbinh T. Nguyen|author3=Lynda K. Johnson|author4=Marc A. Hillmyer|author5=Gregory C. Fu}}</ref><ref>{{cite web|last=Grubbs|first=Robert H.|title=Imidazolidine-based metal carbene metathesis catalysts |url=https://patents.google.com/patent/WO2000071554A2/en28|work=World Intellectual Property Organization|access-date=20 April 2017|author2=Matthias Scholl}}</ref> |
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In 1999, ] showed that alkoxybenzylidene ligand based Ru catalysts offered higher activity and better stability than their Grubbs counterparts without these ligands.<ref name=kingsbury>{{cite journal |last1=Kingsbury |first1=J. S. |last2=Harrity|first2= J. P. A.|last3=Bonitatebus|first3=P. J. |last4=Hoveyda|first4=A. H.|year=1999 |title=A Recyclable Ru-Based Metathesis Catalyst |journal=] |volume=121 |issue=4 |pages=791–799 |doi=10.1021/ja983222u }} |
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== Second generation catalyst== |
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</ref><ref>{{cite web|last=Hoveyda|first=Amir H.|title=Recyclable metathesis catalysts |url=https://patents.google.com/patent/US20020107138|work=United States Patent and Trademark Office|access-date=20 April 2017|author2=Jason Kingsbury|author3=Steven Garber|author4=Brian Gray|author5=John Fourkas}}</ref> Later, Grela (2002) and ] (2003) further improved catalyst activity by incorporating substitution to Hoveyda’s alkoxybenzylidene ligands.<ref name=grela>{{cite journal |last1=Grela |first1=K. |last2=Harutyunyan|first2= S.|last3=Michrowska|first3=A. |year=2002 |title=A Highly Efficient Ruthenium Catalyst for Metathesis Reactions |journal=] |volume=41 |issue=21 |pages=4038–4040|doi=10.1002/1521-3773(20021104)41:21<4038::AID-ANIE4038>3.0.CO;2-0 |pmid=12412074 |url=https://pure.rug.nl/ws/files/3040319/2002AngewChemIntEdGrela.pdf |hdl=11370/969f537e-6d3b-425c-abfa-1b41e7d0e330 |s2cid=262002432 |hdl-access=free }} |
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The Second Generation Catalyst has the same uses in organic synthesis as the First Generation Catalyst, but has a higher activity. This catalyst is stable toward ] and ], thus is easier to handle in the lab. A catalyst based on an '''unsaturated''' N-heterocyclic carbene (1,3-bis(2,4,6-trimethylphenyl)dihydroimidazole) was reported in March 1999 by Nolan's group.<ref name=huang>{{cite journal|title=Olefin Metathesis-Active Ruthenium Complexes Bearing a Nucleophilic Carbene Ligand|author=Jinkun Huang,, Edwin D. Stevens,, Steven P. Nolan,, and, Jeffrey L. Petersen|journal=] |year=1999| volume=121 |issue=12| pages=2674–2678 | doi=10.1021/ja9831352}}</ref> Grubbs' group reported a catalyst based on a saturated N-heterocyclic carbene (1,3-bis(2,4,6-trimethylphenyl)imidazolidine) later the same year <ref name=scholl/> (August 1999). One phosphine ] is replaced with an ] (NHC) and in this case ruthenium is coordinated to two carbene groups. The ] name of the Second Generation Catalyst is benzylidenedichloro(tricyclohexylphosphine)ruthenium. Both generations of the catalyst are commercially available. |
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</ref><ref>{{cite web|last=Blechert|first=Siegfried|title=Novel transition metal complexes and their use in transition metal-catalysed reactions |url=https://patents.google.com/patent/US20030220512|work=United States Patent and Trademark Office|access-date=20 April 2017}}</ref> Zhan’s catalysts were first reported in 2007, and include electron-withdrawing groups like dimethylsulfonamide on the aryl ring. Zhan's second generation catalysts are also tethered to a resin or PEG-linked support via the sulfonamide group on the isopropoxystyrene.<ref name="zhan" /> |
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== Hoveyda-Grubbs Catalyst == |
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In the first generation ''']-Grubbs Catalyst''', one of the ] ligands is replaced by an isopropyloxy group attached to the benzene ring. Its second generation has the other phosphine ligand replaced by NHC. |
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As with other Grubbs-type catalysts with modified chelating benzylidenes, after one catalytic turnover, the chelate is no longer associated with the propagating catalyst, meaning that the initiate rate, the rate of o-alkoxystyrene rechelation, and the rates of various catalyst decomposition events are the factors that differ between the Zhan catalysts and the parent Hoveyda–Grubbs catalysts. A mechanistic study by Plenio and coworkers in 2012 suggested that the Zhan compounds, like other Hoveyda-type catalysts, initiate by competing dissociative and interchange mechanisms, with the relative activation energies being a function of catalyst structure, olefin identity, and reaction conditions.<ref name=plenio>{{cite journal |last1=Thiel |first1=V. |last2=Hendann|first2= M. | last3=Wannowius| first3=K-J. |last4=Plenio|first4=H.|year=2012 |title=On the mechanism of the initiation reaction in Grubbs-Hoveyda complexes|journal=] |volume=134 |issue=2 |pages=1104–1114 |doi=10.1021/ja208967h|pmid= 22188483 }} |
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In one study a water soluble Grubbs catalyst is prepared by attaching a ] chain to the ] group. The imidazolinium salt is deprotonated by ] (KHMDS) ''in situ'' to give the ], which displaces one phosphine ligand to give the modified ruthenium complex:<ref name=hong>{{cite journal|title=Highly Active Water-Soluble Olefin Metathesis Catalyst| author=Soon Hyeok Hong and Robert H. Grubbs|journal= ]| year=2006| volume=128|issue=11 |pages=3508–3509| doi=10.1021/ja058451c|pmid=16536510}}</ref> |
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</ref> However, nobody had been able to rigorously establish through experimentation how the various changes to the structure affected catalytic activity of the complex. Engle, Luo, Houk, Grubbs, and coworkers developed a model that could rationalize initiation rates of ruthenium olefin metathesis catalysts with chelated benzylidenes, using a combination of organometallic synthesis, reaction kinetics, NMR spectroscopy, X-ray crystallography, and DFT calculations.<ref name=engle>{{cite journal |last1=Engle |first1=K. M. |last2=Lu|first2= G. | last3=Luo| first3=S-X. |last4=Henling|first4=L. M.|last5=Takase|first5=M. K.|last6=Liu|first6=P.|last7=Houk|first7=K. N.|last8=Grubbs|first8=R. H.|year=2015 |title=Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes|journal=] |volume=137 |issue=17 |pages=5782–5792 |doi=10.1021/jacs.5b01144 |pmid=25897653 |url=https://resolver.caltech.edu/CaltechAUTHORS:20150428-085409439 }} |
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</ref> |
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== Preparation == |
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In order to make the catalysts, the pre-complex is treated with CuCl and the isopropoxystyrene ligand.<ref name="zhan" /> |
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This catalyst is used in the ] reaction in water of a diene carrying an ] group making it water-soluble as well. |
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The isopropoxystyrene ligand is prepared using an ''ortho''-vinylation of the phenol with ethyne, using conditions first proposed by Masahiko Yamaguchi in 1998. Here, SnCl<sub>4</sub> and Bu<sub>3</sub>N were added to ethyne to generate stannylacetylene, which is the active vinylating species in this C–C bond formation.<ref name=yamaguchi>{{cite journal |last1=Yamaguchi |first1=M. |last2=Arisawa|first2= M.|last3=Omata|first3=K.|last4=Kuninobu|first4=K.|last5=Hirama|first5=M.|last6=Uchimaru|first6=T. |year=1998 |title=''Ortho''-Vinylation Reaction of Phenols with Ethyne |journal=] |volume=63 |issue=21 |pages=7298–7305|doi=10.1021/jo980785f |pmid=11672375 }} |
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</ref> After coupling, the phenol can be alkylated using ''i''-PrBr and a base. |
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== Applications == |
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An interesting application of Grubbs' Catalyst is in the aerospace industry. A spaceship's ] is a necessarily very strong material, but over time microcracks in the structure can form. A new material, with potential application in the construction of spaceship hulls, contains Grubbs' Catalyst, as well as capsules of ], which can undergo ]. When a crack in the hull forms, the capsules are ruptured and come into contact with Grubbs' Catalyst, which ] dicyclopentadiene and seals the crack.<ref name=white>{{cite journal|author=S.R. White, N.R. Sottos, P.H. Geubelle, J.S. Moore, M.R. Kessler, S.R. Sriram, E.N. Brown, S. Viswanathan| doi=10.1038/35057232| journal=]|year= 2001 |volume= 409| pages= 794–797|title= Autonomic healing of polymer composites|pmid=11236987|issue=6822}}</ref> |
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== Recycling == |
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On October 5, 2005, ], ] and ] won the ] in recognition of their contributions to the development of this widely used process. |
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The Zhan catalysts can be recovered and recycled by simple precipitation or filtration. Zhan Catalyst-1B and -1C are soluble in dichloromethane, dichloroethane, chloroform, ether, and other solvents, but insoluble in methanol, ethanol, and other alcohols. Zhan Catalyst-II is linked to a resin- and PEG-linked support, offering a great advantage in recyclable utility, and leaving little or no trace of metal contamination within the product of olefin metathesis reactions. These catalysts can then be reused.<ref name="zhan" /> |
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==References== |
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==References== |
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{{Reflist}} |
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{{Reflist|30em}} |
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<!-- # {{Note|Louie}} Louie, J.; Grubbs, R. H. . --> |
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{{Ruthenium compounds}} |
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{{Ruthenium compounds}} |
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{{DEFAULTSORT:Grubbs' Catalyst}} |
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{{DEFAULTSORT:Zhan's Catalyst}} |
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