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obstacle to the use of Shvo's catalyst in the hydrogenation of alkynes is its propensity to bind the alkyne quite tightly, forming a stable complex that gradually poisons the catalyst. Intramolecular reactions proceed as well, illustrated by the conversion of allylic alcohols to ketones. Shvo's catalyst also catalyzes dehydrogenations.
35:
511:
In the presence of a suitable hydrogen donor or hydrogen gas, Shvo's catalyst effects the hydrogenation of several polar functional groups, e.g. aldehydes, ketones, imines, and iminium ions. Many alkenes and ketones undergo hydrogenation, although conditions are forcing: 145 °C (500 psi). One
528:
The mechanism of hydrogenation catalyzed by Shvo's catalyst has been a matter of debate, broadly between two alternative descriptions of the double bond's interaction with the complex at the rate-determining step. The proposed alternatives are an inner-sphere mechanism, where the transition state
504:
529:
involves interaction with the metal only, and an outer-sphere mechanism, in which the cyclopentadienol proton also interacts with the substrate. Kinetic isotope studies provide evidence of a concerted transfer due to strong rate influence from both the ligand -OH and the metal hydride.
567:
Another case of "hydrogen borrowing", the alkylation of amines using other amines is also promoted by Shvo's catalyst. The reaction proceeds through oxidation to an imine, which allows nucleophilic attack, followed by an elimination step and reduction of the double bond.
516:
335:
of polar functional groups including aldehydes, ketones and imines. The compound is of academic interest as an early example of a catalyst for transfer hydrogenation that operates by an "outer sphere mechanism". Related derivatives are known where
1014:
805:
Choi, Jun Ho; Kim, Namdu; Shin, Yong Jun; Park, Jung Hye; Park, Jaiwook (June 2004). "Heterogeneous Shvo-type ruthenium catalyst: dehydrogenation of alcohols without hydrogen acceptors".
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replaces some of the phenyl groups. Shvo's catalyst represents a subset of homogeneous hydrogenation catalysts that involves both metal and ligand in its mechanism.
919:
174:
InChI=1S/C29H21O.C29H20O.4CO.2Ru/c2*30-29-27(23-17-9-3-10-18-23)25(21-13-5-1-6-14-21)26(22-15-7-2-8-16-22)28(29)24-19-11-4-12-20-24;4*1-2;;/h1-20,30H;1-20H;;;;;;
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Conley, Brian L.; Pennington-Boggio, Megan K.; Boz, Emine; Williams, Travis J. (2010). "Discovery, Applications, and
Catalytic Mechanisms of Shvo's Catalyst".
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Samec, Joseph S. M.; Bäckvall, Jan-E. (2008). "Hydroxytetraphenylcyclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)hydrotetracarbonyldiruthenium(II)".
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Bäckvall, Jan-E.; Andreasson, Ulrika (January 1993). "Ruthenium-catalyzed isomerization of allylic alcohols to saturated ketones".
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198:#.#.#.#.C1=CC=C(C=C1)C2=C(C(=O)C(=C2C3=CC=CC=C3)C4=CC=CC=C4)C5=CC=CC=C5.C1=CC=C(C=C1)2(((2C3=CC=CC=C3)O)C4=CC=CC=C4)C5=CC=CC=C5..
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1-Hydroxytetraphenylcyclopentadienyl-(tetraphenyl-2,4-cyclopentadien-1-one)-μ-hydrotetracarbonyldiruthenium(II)
383:. Subsequent hydrogenation of this tricarbonyl affords Shvo's catalyst. The iron analogue is also known, see
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Shvo, Y.; Czarkie, D.; Rahamim, Y. (1986). "A new group of ruthenium complexes: structure and catalysis".
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The compound contains a pair of equivalent Ru centres that are bridged by a strong hydrogen bond and a
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Conley, Brian L.; Williams, Travis J. (2010). "Dehydrogenation of ammonia-borane by Shvo's catalyst".
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653:. Tetrahedron Lett. 22(16) 1981, pp. 1541-1544. Blum, Y.; Shvo, Y. Isr. J. Chem. 1984, 24, 144.
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Structure of proposed intermediate in transfer hydrogenation of a ketone by Shvo's catalyst.
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The catalyst is named after Youval Shvo, who uncovered it through studies on the effect of
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665:"Synthesis of (R)-2-Methoxy-N-(1-Phenylethyl)Acetamide via Dynamic Kinetic Resolution"
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Hollmann, D.; Bahn, S.; Tillack, A.; Beller, M. Angew. Chem. Int. Ed. 2007, 46, 8291.
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Products obtained from amination of a propargylic alcohol using Shvo's catalyst.
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Except where otherwise noted, data are given for materials in their
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Lisa Kanupp Thalén, Christine Rösch, Jan-Erling Bäckvall (2012).
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hydride. In solution, the complex dissociates unsymmetrically:
552:
Addition of the amine is facilitated through oxidation to the
645:
Y. Blum, D. Reshef, and Y. Shvo. H-transfer catalysis with Ru
507:
Example of hydrogenation of a carbonyl using Shvo's catalyst.
263:
223 to 227 °C (433 to 441 °F; 496 to 500 K)
563:
Example of alkylation of an amine using Shvo's catalyst.
519:
Example of an imine hydrogenation using Shvo's catalyst.
299:
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Blum, Y.; Shvo, Y. J. Organomet. Chem. 1984, 263, 93.
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712:Encyclopedia of Reagents for Organic Synthesis
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695:: CS1 maint: multiple names: authors list (
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356:. The reaction of diphenylacetylene and Ru
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840:Haak, E. Eur. J. Org. Chem. 2007, 2815.
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456:{\displaystyle {\ce {<<=>}}}
177:Key: LYADOKFHMFDLJK-UHFFFAOYSA-N
7:
141:
25:
537:Shvo's catalyst facilitates the
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42:
33:
352:on the catalytic properties of
285:(at 25 °C , 100 kPa).
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430:
1:
757:10.1016/S0040-4039(00)73934-7
819:10.1016/j.tetlet.2004.04.113
354:triruthenium dodecacarbonyl
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720:10.1002/047084289X.rn01063
1508:Organoruthenium compounds
714:. John Wiley & Sons.
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32:
682:10.15227/orgsyn.089.0255
329:organoruthenium compound
1518:Hydrogenation catalysts
772:Chemical Communications
491:Hydrogenation catalysis
344:Synthesis and structure
275:polar organic solvents
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508:
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245:1085.13
421:
886:Ruthenium compounds
807:Tetrahedron Letters
745:Tetrahedron Letters
641:10.1021/ja00283a041
539:Tishchenko reaction
366:piano stool complex
331:that catalyzes the
270:Solubility in water
29:
18:Shvo's complex
1513:Carbonyl complexes
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312:Infobox references
27:
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1494:
813:(24): 4607–4610.
751:(34): 5459–5462.
669:Organic Syntheses
629:J. Am. Chem. Soc.
605:10.1021/cr9003133
450:
350:diphenylacetylene
320:Chemical compound
318:
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107:Interactive image
16:(Redirected from
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259:Melting point
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66:Identifiers
250:Appearance
207:Properties
83:104439-77-2
1502:Categories
1225:Ru(II,III)
572:References
471:OH)RuH(CO)
364:gives the
241:Molar mass
118:ChemSpider
94:3D model (
73:CAS Number
57:IUPAC name
524:Mechanism
447:⇀
439:−
431:↽
377:CO)Ru(CO)
1477:Ru(VIII)
1103:Ru(SO(CH
975:H(Ru(CO)
792:20508879
613:20095576
483:O)Ru(CO)
392:bridging
152:56845452
127:26606435
1446:Ru(VII)
1241:Ru(III)
1055:(Ru((NC
675:: 255.
305:what is
303: (
235:
139:PubChem
1427:Ru(VI)
1326:Ru(IV)
1079:Ru(P(C
992:Ru(II)
920:Ru(P(C
900:Ru(CO)
790:
726:
611:
327:is an
300:verify
297:
191:SMILES
51:Names
1408:Ru(V)
1373:BaRuO
1341:SrRuO
1311:Ru(NO
1248:Ru(CH
1155:RuClC
1139:CH(CH
1123:(RuCl
948:Ru(I)
893:Ru(0)
554:ynone
414:H(CO)
338:tolyl
166:InChI
96:JSmol
1381:RuCl
1296:RuBr
1288:RuCl
1260:Ru(O
1252:COO)
1163:(P(C
1019:Ru(N
999:RuCl
936:(CO)
912:(CO)
788:PMID
724:ISBN
697:link
649:(CO)
609:PMID
475:+ (C
360:(CO)
323:The
1484:RuO
1465:RuO
1453:N(C
1434:RuF
1415:RuF
1390:RuF
1365:RuO
1353:RuO
1333:RuO
1304:RuI
1280:RuF
1071:)Cl
1007:RuB
815:doi
780:doi
753:doi
716:doi
677:doi
637:doi
633:108
601:doi
597:110
410:HRu
369:(Ph
142:CID
1504::
1361:Li
1349:Sr
1232:Cl
1216:Ru
1204:(C
1199:Ru
1191:Cl
1189:72
1185:43
1135:CH
1115:Cl
1095:Cl
1039:SO
1031:(C
1025:12
1015:Na
971:O)
959:(C
955:(C
914:12
908:Ru
811:45
809:.
786:.
776:46
774:.
749:34
747:.
722:.
693:}}
689:{{
673:89
671:.
667:.
651:12
607:.
595:.
579:^
479:Ph
467:Ph
406:O)
402:Ph
398:(C
387:.
362:12
336:p-
231:Ru
225:42
221:62
1486:4
1467:4
1463:4
1461:)
1459:7
1457:H
1455:3
1436:6
1417:5
1395:4
1383:4
1375:3
1367:3
1363:2
1355:4
1351:2
1343:3
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