246047-72-3

Basic information

• Product Name: GRUBBS CATALYST 2ND GENERATION
• Synonyms: 1,3-Bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorophenylmethylene)(tricyclohexylphosphine)ruthenium, Benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(tricyclohexylphosphine)ruthenium, (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium;Grubb's second generation catalyst,97%;Grubbs Catalyst 2nd Generation,97+%;Benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(tricyclohexyl-phosphine) ruthenium;(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium ,97%;(1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium ,95%;Grubbs Catalyst, 2nd Generation,(1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, 1,3-Bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene;1,3-Bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlo
• CAS NO: 246047-72-3
• Molecular Formula: C₄₆H₆₅Cl₂N₂PRu
• Molecular Weight: 848.97
• EINECS: 1312995-182-4
• Product Categories: Ru
• Mol File: 246047-72-3.mol
• Article Data: 15

Chemical Properties

• Melting Point: 143.5-148.5 °C(lit.)
• Appearance: pink-brown to red-purple crystals or powder
• Storage Temp.: 2-8°C
• CAS DataBase Reference: GRUBBS CATALYST 2ND GENERATION(CAS DataBase Reference)
• NIST Chemistry Reference: GRUBBS CATALYST 2ND GENERATION(246047-72-3)
• EPA Substance Registry System: GRUBBS CATALYST 2ND GENERATION(246047-72-3)

Safety Data

• Hazard Codes: F
• Statements: 36/37/38-11
• Safety Statements: 26-36/37/39
• RIDADR: 1325
• WGK Germany: 3
• F: 10-23
• HazardClass: 4.1
• PackingGroup: Ⅱ
• Hazardous Substances Data: 246047-72-3(Hazardous Substances Data)

Usage

Description

Grubbs catalysts are a series of transition metal carbene complexes used as catalyst for olefin metathesis.1 The Grubbs catalysts are based on a ruthenium atom surrounded by five ligands: two neutral electron-donating entities (e.g., trialkylphosphines, N-heterocyclic carbenes), two monoanionic groups (e.g., halides), and one alkylidene moiety (e.g., unsubstituted and substituted methylidenes). L2X2Ru=CHR complexes (where L is a phosphine ligand) were discovered first and are referred to as the first-generation Grubbs catalyst. (L)(L’)X2Ru=CHR complexes (where L is a phosphine ligand and L’ a saturated N-heterocyclic carbene or NHC ligand) are referred to as the second-generation Grubbs catalysts. The first-generation Grubbs catalysts show attractive functional-group tolerance and handling properties and have been widely used as highly efficient promoters for ring opening metathesis polymerizations, ring-closing metathesis reactions to make disubstituted olefins, ethenolysis (i.e., cleavage of the carbon–carbon double bond), cross-metathesis of terminal olefins, and the preparation of 1,3-dienes via enyne metathesis. These catalysts and analogues are still widely used in important processes, including the ethenolysis of feedstocks derived from bio-renewable seed oils and the manufacture of macrocyclic hepatitis C therapeutics. Nevertheless, the first-generation Grubbs catalysts show limitations with electron-poor and electron-rich double bonds as well as with sterically hindered systems.?The second-generation Grubbs catalysts with excellent metathesis activity while retaining the handling characteristics and broad functional-group tolerance of the earlier Grubbs catalysts are thereby developed. At the same time, the second-generation catalysts are stable against moisture and air.

Reference

M. L. Crawley, B. M. Trost, Applications of Transition Metal Catalysis in Drug Discovery and Development, 2012, ISBN 978-0-470-63132-4

Chemical Properties

pink-brown to red-purple crystals or powder

Characteristics

Grubbs catalyst is a kind of coordination compound used in olefin metathesis reaction, and the ligand in it has a great influence on the catalytic performance and stability of the catalyst. Grubbs second-generation catalysts are more active than first-generation catalysts and have a wider substrate range, including sterically demanding or deactivated olefins such as 1,1-disubstituted olefins and α,β-non- Saturated carbonyl compounds.

Uses

Different sources of media describe the Uses of 246047-72-3 differently. You can refer to the following data:
1. suzuki reaction
2. Grubbs Catalyst? M204 can be used as a catalyst for ring-closing metathesis (RCM), cross-metathesis, and ring-opening metathesis polymerization (ROMP). It is also used to synthesize trisubstituted olefins with excellent functional group tolerance and selectivity via cross-metathesis and ring closing metathesis reactions.It can also be used as a catalyst:To synthesize coumarins from phenolic compounds via RCM.To cleave secondary (E)-allyl vic-diols to aldehydes.

Synthetic route

Grubbs catalyst first generation + 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene (173035-11-5) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In tetrahydrofuran at 25℃; for 2h; Inert atmosphere; Glovebox;	94%

1,3-di(2,4,6-trimethylphenyl)-2-(pentafluorophenyl)-2,4,5-trihydroimidazole (782479-45-2) + Grubbs catalyst first generation → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In toluene mixt. of Ru complex and imidazolidine in toluene was heated at 60°C for 4 h;	91%

Grubbs catalyst first generation + 1,3-bis(2,4,6-trimethylphenyl)-2-(trichloromethyl)imidazolidine (260054-47-5) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In toluene mixt. of Ru complex and imidazolidine in toluene was heated at 60°C for 4 h;	87%
In toluene byproducts: PCy3, CHCl3; (N2); using Schlenk techniques; mixing of (Mes2C3N2H5)(CCl3) and (PCy3)2Cl2Ru(CHPh) in toluene; heating at 60°C for 90 min; cooling to room temp., removal of solvent under vac., washing with methanol and pentane, drying under vac. for 12 h;	84%

RuCl2(sIMes)(CHPh)(pyridine)2 + tris(cyclohexyl)phosphonium tetrafluoroborate (58656-04-5) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In toluene byproducts: pyridinium tetrafluoroborate, pyridine; 1.1 equiv. of phosphonium salt; passage through silica plug;	80%

Grubbs catalyst first generation + 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride (173035-10-4) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
With KO(C(CH3)3) In hexane byproducts: KCl, C(CH3)3OH, PCy3; using Schlenk techniques; mixing of (Mes2C3N2H5)(Cl), KO(t-Bu) and (PCy3)2Cl2Ru(CHPh) in anhyd. hexane; degassing of soln. by pulling vac. for afew minutes, heating at 60°C for 24 h in vac. with very vigorous stirring; cooling to room temp., opening the flask to air, addn. of 1:1 2-propanol:water; stirring in air for 30 min, filtration, washing with 2-propanol:water and with hexane, drying under vac. overnight, elem. anal.;	75%
With potassium tert-butylate In hexane at 60℃; for 24h; Schlenk technique;	75%
With KOC(CH3)3 In toluene mixing N compd., Ru complex, K compd. in toluene at 50°C;

Grubbs catalyst first generation + N,N'-dimesityl-4,5-dihydro-1H-imidazolium tetrafluoroborate → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Stage #1: N,N'-dimesityl-4,5-dihydro-1H-imidazolium tetrafluoroborate With potassium tert-butylate In tetrahydrofuran at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: Grubbs catalyst first generation In benzene at 80℃; for 1.5h; Schlenk technique; Inert atmosphere;	56%
With KO(C(CH3)3) In benzene byproducts: KBF4, C(CH3)3OH, PCy3; (N2); using Schlenk techniques; mixing of (Mes2C3N2H5)(BF4), KO(t-Bu) and THF; stirring for 1 h; addn. of (PCy3)2Cl2Ru(CHPh) in benzene; heatingat 80°C for 30 min; removal of volatiles under vac., suspending in benzene, filtration over Celite, concn., addn. of methanol, pptn., washing with methanol, pentaneand then drying under vac.;	45%

RuCl2(sIMes)(CHPh)(pyridine)2 + tricyclohexylphosphine (2622-14-2) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
With C5((2)H)5N In not given under Ar or N2; Ru complex reacts instantaneously with the phosphine; addn. of an excess of C5((2)H)5N leads to a formation of the bis(pyridine-d5) complex; evapn. of volatiles in vac. leads to a reformation of the phosphine complex;

Grubbs catalyst first generation + bis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)ruthenium(II) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In benzene-d6 (N2); using Schlenk techniques; charging of NMR tube with Ru(CHPh)Cl2(C3N2H4Mes2)2, (PCy3)2(Cl)2Ru(CHPh) (1 equiv.) and C6D6; heating at 70°C for 47 h; monitoring by NMR;

bis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)ruthenium(II) + tricyclohexylphosphine (2622-14-2) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In benzene-d6 (N2); using Schlenk techniques; charging of NMR tube with Ru(CHPh)Cl2(C3N2H4Mes2)2, PCy3 (excess) and C6D6; heating at 80°C for 36 h; monitoring by NMR;

styrene (292638-84-7) + [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In tetrahydrofuran excess styrene;	0%
In toluene excess styrene;	0%

(N,N'-dimesityl-N,N'-dimethylformamidin-2-ylidene)(1,3-dimesitylimidazolin-2-ylidene)Cl2Ru=CHPh + tricyclohexylphosphine (2622-14-2) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In benzene-d6 100°C, 8 h;

(N,N'-bis(2,6-di-isopropylphenyl)-N,N'-dimethylformamidin-2-ylidene)(1,3-dimesitylimidazolin-2-ylidene)Cl2Ru=CHPh + tricyclohexylphosphine (2622-14-2) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In benzene-d6 100°C, 2 h;

2,4,6-trimethylaniline (88-05-1) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: isopropyl alcohol; water / 24 h / 0 - 20 °C 2: sodium tetrahydroborate; hydrogenchloride / water; tetrahydrofuran / 0 - 20 °C 3: formic acid / 5 h / 120 °C / Inert atmosphere 4: potassium tert-butylate / hexane / 24 h / 60 °C / Schlenk technique View Scheme

N,N'-bis(2,4,6-trimethylphenyl)ethanediimine (56222-36-7) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium tetrahydroborate; hydrogenchloride / water; tetrahydrofuran / 0 - 20 °C 2: formic acid / 5 h / 120 °C / Inert atmosphere 3: potassium tert-butylate / hexane / 24 h / 60 °C / Schlenk technique View Scheme

N1,N2-dimesitylethane-1,2-diaminium chloride (258278-23-8) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: formic acid / 5 h / 120 °C / Inert atmosphere 2: potassium tert-butylate / hexane / 24 h / 60 °C / Schlenk technique View Scheme

(SIMes)Ru(S-DMSO)(CHPh)Cl2 + tricyclohexylphosphine (2622-14-2) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
for 0.5h; Inert atmosphere; Schlenk technique;

dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylylidene)(benzylidene)bis(pyridine)ruthenium(II) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: NaN(Si(CH3)3)2 / toluene 2: benzene-d6 View Scheme

1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride (173035-10-4) → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium hexamethylsilazane / toluene / 1 h / 20 °C / Inert atmosphere; Schlenk technique 2: toluene / Schlenk technique; Inert atmosphere View Scheme

Grubbs catalyst first generation + 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene → tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3)

Conditions	Yield
In toluene Schlenk technique; Inert atmosphere;

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + (4-isopropoxy-3-vinyl-phenyl)dimethyl-phosphoramidate ethyl ester → 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-isopropoxy)-5-(N,N-dimethylamino-ethylphosphite)phenyl]methyleneruthenium(II) dichloride

Conditions	Yield
With copper(l) chloride In dichloromethane at 30℃; for 1h; Schlenk technique;	100%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + dmap (1122-58-3) → (IMesH2)(C7H10N2)2(Cl)2Ru=CHPh

Conditions	Yield
In toluene at 20 - 25℃; for 12h;	99%
In neat (no solvent) for 0.333333h; Milling;	87%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + hydrogen (1333-74-0) + ethylenediamine (107-15-3) → [RuHCl(NH2CH2CH2NH2)(P(C6H11)3)(C3H4N2(C6H2(CH3)3)2)]

Conditions	Yield
In sodium hydroxide under H2 (1 atm.); NMR;	99%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + (4-isopropoxy-3-vinylphenyl)(diphenyl)methanol (934165-44-3) → ((2,4,6-trimethylphenyl)2(C3H4N2))Cl2Ru(CH(C6H3)(OC3H7)(5-C(OH)Ph2))

Conditions	Yield
With copper(l) chloride In dichloromethane carbene complex (0.075 mmol), CuCl (0.09 mmol), and CH2Cl2 (4 ml) placedin Schlenk tube; styrene (0.09 mmol) in CH2Cl2 added; stirred (under Ar , 40°C, 1 h); concd. (vac.); column chromy. (silica gel, cyclohexane/ethyl acetate 3:1); green band removed; evapd.; washed with min. amt. of cold n-pentane; dried (vac.);	99%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 1-(4-isopropoxy-3-vinylphenyl)-pyridinium hexafluorophosphate → (C3H4N2(C6H2(CH3)3)2)RuCl2(CHC6H3(NC5H5)OCH(CH3)2)(1+)*PF6(1-)=((C3H4N2(C6H2(CH3)3)2)RuCl2(CHC6H3(NC5H5)OCH(CH3)2))PF6

Conditions	Yield
With copper(l) chloride In dichloromethane under Ar; soln. of pyridinium compd. in CH2Cl2 added to Ru complex and CuCl (molar ratio 1.2:1:1.5) in CH2Cl2; stirred at 45°C for 15 min; under air; concd. in vac.; EtOAc added; soln. filtered off; solvent removed; washed with cold n-pentane; dried under vac.;	99%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + C2H4OS2(2-)*2Li(1+) → [ruthenium(III)(O(CH2CH2S)2)(CHPh)(1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazole)]

Conditions	Yield
In tetrahydrofuran for 16h; Inert atmosphere; Schlenk technique;	99%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + (LiSCH2CH2)2O·2THF → Ru(Mes2Im)(=CHPh)[O(CH2CH2S)2]

Conditions	Yield
In toluene; acetonitrile for 16h; Inert atmosphere; Schlenk technique; Glovebox;	99%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2C4H8O*C4H8S3(2-)*2Li(1+) → Ru(Mes2Im)(=CHPh)[O(CH2CH2S)2]

Conditions	Yield
In tetrahydrofuran	98%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2Li(1+)*SCH2CH2SCH2CH2S(2-)=LiSCH2CH2SCH2CH2SLi → (SIMes)Ru(CHPh)(SCH2CH2)2S

Conditions	Yield
In toluene; acetonitrile for 16h; Inert atmosphere; Schlenk technique; Glovebox;	98%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + Vinylidene fluoride (75-38-7) → 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene-dichloro(phenylmethylene)-(tricyclohexyl-phosphine)difluoromethylene ruthenium

Conditions	Yield
In benzene under 1140.08 Torr; for 12h; Heating;	98%
In benzene soln. of Ru(Cl)2(P(C6H11)3)(CH(C6H5))(C3H5N2(C6H2(CH3)3)2) in dry degassed benzene in thick-walled glass ampule put under approx. 1.5 atm of 1,1-difluoroethylene; mixt. heated at 60°C for 12 h; color changed from reddish to brown; soln. concd. and purifed by column chromy. in air (silica gel, 5:1 pentane:THF); orange fraction stripped of solvent; dried under vac.;	86%
In benzene-d6 at 60℃; under 760.051 Torr; for 12h;
In benzene-d6 at 60℃; under 760.051 Torr; for 12h;

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + p-phenylpyridine (939-23-1) → (IMesH2)(C11H9N)2(Cl)2Ru=CHPh

Conditions	Yield
In toluene at 20 - 25℃; for 12h;	97%
In toluene at 20 - 25℃; for 12h;	97%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + C21H23NO3S → C42H49Cl2N3O3RuS

Conditions	Yield
In dichloromethane at 45℃;	97%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2-methyl-8-vinylquinoline (261899-66-5) → [RuCl2(ImH2Mes)((2-methyl-8-quinolinyl)methylene)]

Conditions	Yield
With copper(l) chloride In dichloromethane at 30℃; for 1.5h;	96%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 1,10-Phenanthroline (66-71-7) → (IMesH2)(C12H8N2)(Cl)2Ru=CHPh

Conditions	Yield
In toluene at 20 - 25℃; for 12h;	96%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + silver trifluoromethanesulfonate (2923-28-6) + acetonitrile (75-05-8) → [(MeCN)3(H2IMes)(benzylidene)ruthenium](triflate)2

Conditions	Yield
In chloroform byproducts: AgCl, PCy3; using standard Schlenk techniques; mixt. of Ru complex and Ag salt (2 equiv.) in CHCl3 stirred in presence of MeCN (3 equiv.) at 25°C for30 min; filtered; n-pentane added to filtrate; filtered; ppt. washed with n-pentane; dried under vac.; elem. anal.;	96%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + C16H14FNO → C36H38Cl2FN3ORu

Conditions	Yield
With copper(l) chloride In dichloromethane at 20℃; for 0.5h; Inert atmosphere;	96%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + iodine (7553-56-2) → 5I(1-)*C2H6*C46H64Cl2N2PRu(1+)*I5(1-)

Conditions	Yield
In dichloromethane at 25℃; for 0.5h; Inert atmosphere;	95%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) → (2R,4aR,5aS,10aR,11R,11aS)-2-(naphthalen-2-yl)-4,4a,5a,6,9,10a,11,11a-octahydro-[1,3]dioxino[40,50:5,6]pyrano[3,2-b]oxepin-11-ol (784157-67-1)

Conditions	Yield
With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃; for 5h;	95%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + acetonitrile (75-05-8) → C32H38Cl2N4Ru

Conditions	Yield
With copper(l) chloride at 20℃; for 3h;	95%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + C17H17NO3S → C37H41Cl2N3O3RuS

Conditions	Yield
In dichloromethane at 45℃;	95%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 3-Bromopyridine (626-55-1) → Grubbs catalyst third generation (477218-66-9)

Conditions	Yield
Inert atmosphere;	94%
In not given byproducts: P(C6H11)3; within minutes; pptn. with pentane;	89%
at 20 - 25℃; for 12h;	86%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2-(prop-1-enyl)phenol (6380-21-8) → C46H64ClN2OPRu

Conditions	Yield
With tricyclohexylphosphine In dichloromethane at 40℃; for 24h; Inert atmosphere; Schlenk technique;	94%
With tricyclohexylphosphine In dichloromethane at 40℃; for 5h;	72%
With tricyclohexylphosphine In dichloromethane at 40℃; for 5h;	72%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2-(prop-1-enyl)phenol (6380-21-8) + tricyclohexylphosphine (2622-14-2) → C46H64ClN2OPRu

Conditions	Yield
In dichloromethane at 40℃; for 24h; Inert atmosphere;	94%

N-(but-3-enyl)-4-methyl-N-(phenylethynyl)benzenesulfonamide (853688-25-2) + tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) → C40H45Cl2N3O2RuS

Conditions	Yield
In dichloromethane at 45℃;	94%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2,2'-biquinoline (119-91-5) → (IMesH2)(C18H12N2)2(Cl)2Ru=CHPh

Conditions	Yield
In toluene at 20 - 25℃; for 12h;	93%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 4-pyrrolidin-1-ylpyridine (2456-81-7) → (IMesH2)(C9H12N2)2(Cl)2Ru=CHP

Conditions	Yield
at 20 - 25℃; for 12h;	93%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + ethyl vinyl ether (109-92-2) → RuCl2(ethoxymethylidene)(1-mesityl-3-mesityl-4,5-dihydroimidazol-2-ylidene)(PCy3)

Conditions	Yield
In dichloromethane ligand was added to CH2Cl2 soln. of Ru-complex, stirred at room temp. for 2 h under N2; solvent was evapd. under vac., washed with pentane and MeOH;	93%
In benzene-d6 Kinetics; at 25°C; monitoring by NMR;
In toluene at 50℃; for 1h; Schlenk technique; Inert atmosphere;
In (2)H8-toluene at 30℃;

pyridine (110-86-1) + tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) → dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylylidene)(benzylidene)bis(pyridine)ruthenium(II)

Conditions	Yield
In toluene at 20℃; for 0.5h; Inert atmosphere;	92%
In toluene at 20℃; for 0.5h; Inert atmosphere; Glovebox;	92%
In toluene at 20℃; for 0.5h; Inert atmosphere; Glovebox;	92%

tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride (246047-72-3) + 2-hydroxy-5-nitrostyrene (83520-63-2) → C46H63ClN3O3PRu

Conditions	Yield
With tricyclohexylphosphine In dichloromethane at 40℃; for 24h; Inert atmosphere; Schlenk technique;	92%
With tricyclohexylphosphine In dichloromethane at 40℃; for 1h;	50%
With tricyclohexylphosphine In dichloromethane at 40℃; for 1h;	50%

Upstream product

• 2622-14-2 tricyclohexylphosphine 
• 172222-30-9 Grubbs catalyst first generation 
• 173035-10-4 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride 
• 173035-11-5 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene 
• 258278-23-8 N¹,N²-dimesitylethane-1,2-diaminium chloride 
• 56222-36-7 N,N'-bis(2,4,6-trimethylphenyl)ethanediimine 
• 88-05-1 2,4,6-trimethylaniline 
• 58656-04-5 tris(cyclohexyl)phosphonium tetrafluoroborate 
• 100-42-5 styrene 
• 782479-45-2 1,3-di(2,4,6-trimethylphenyl)-2-(pentafluorophenyl)-2,4,5-trihydroimidazole 
• 260054-47-5 1,3-bis(2,4,6-trimethylphenyl)-2-(trichloromethyl)imidazolidine 

Downstream Products

• 301224-40-8 (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)Cl₂Ru=CH-o-OiPrC₆H₄ 
• 36621-70-2 carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) 
• 477218-66-9 Grubbs catalyst third generation  

Relevant articles and documents

Ruthenium-indenylidene complexes: Powerful tools for metathesis transformations

Ruthenium-indenylidene complexes represent a class of robust and efficient pre-catalysts for olefin metathesis reactions. In this feature article, we provide an overview of the various complexes belonging to this family and summarise their use in various applications. The relation between the nature of ancillary ligands around the metal coordination sphere of these complexes and their catalytic activity is also discussed. The Royal Society of Chemistry.

Merrifield resin-assisted routes to second-generation catalysts for olefin metathesis

Phosphine-scavenging resins can significantly facilitate the synthesis of highly active Ru metathesis catalysts, including the second-generation Grubbs, Hoveyda, and indenylidene catalysts (GII, HII, InII). These catalysts are customarily prepared by ligand exchange of the corresponding first-generation catalysts with the N-heterocyclic carbene (NHC) H2IMes. The PCy3 coproduct is conventionally removed by pentane extraction, but the partial solubility of the desired Ru products can cause product losses of over 20%. Sequestration of the PCy3 coproduct with CuCl is more efficient, but is undesirable given the potential for non-innocent copper residues. Use of the arylsulfonic acid resin Amberlyst-15 delivers near-quantitative catalyst yields, but the high acidity of the resin leads to problems with reproducibility and decomposition. An alternative approach is described, in which a neutral Merrifield resin (crosslinked polystyrene with pendant p-C6H4CH2I groups; MF-I) is used to sequester PCy3 as the covalently-tethered benzylphosphonium salt. Addition of MF-I following complete ligand exchange effects quantitative uptake of free PCy3 (and any residual free NHC) within 45 min at RT: the clean products are isolated by filtration, in ca. 95% yield. These yields compare well with those obtained via the Amberlyst-15 route, without the challenges due to resin acidity. The efficacy of this methodology is demonstrated in the synthesis of isotopically-labelled derivatives of HII, in which the H2IMes ligand bears a 13C-label at the carbene carbon, or perdeuterated mesityl rings.

N-Heterocyclic carbene-based ruthenium-hydride catalysts for the synthesis of unsymmetrically functionalized double-decker silsesquioxanes

Ruthenium-N-heterocyclic carbene complexes with the generic formula [RuHCl(CO)(NHC)(PCy3)] exhibit a high catalytic activity toward the (E)-selective silylative coupling of divinyl-substituted double-decker silsesquioxanes with two distinctly substituted styrenes. This process leads to a novel class of unsymmetrically functionalized silsesquioxane derivatives.

Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts

The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.