15243-33-1

Basic information

• Product Name: RUTHENIUM CARBONYL
• Synonyms: dodecacarbonyltri-rutheniutriangulo;Ru3(CO)12;Ruthenium, dodecacarbonyltri-, triangulo;Ruthenium,dodecacarbonyltri-;DODECACARBONYLTRIRUTHENIUM;DODECACARBONYLTRIRUTHENIUM (0);RUTHENIUM CARBONYL;TRIRUTHENIUM DODECACARBONYL
• CAS NO: 15243-33-1
• Molecular Formula: C₁₂O₁₂Ru₃
• Molecular Weight: 639.33
• EINECS: 239-287-4
• Product Categories: Classes of Metal Compounds;Ru (Ruthenium) Compounds;Transition Metal Compounds;metal carbonyl complexes;Ru
• Mol File: 15243-33-1.mol
• Article Data: 175

Chemical Properties

• Melting Point: 150 °C
• Appearance: orange/crystal
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: Sparingly soluble in hydrocarbons (e.g. hexane, cyclohexane, ben
• CAS DataBase Reference: RUTHENIUM CARBONYL(CAS DataBase Reference)
• NIST Chemistry Reference: RUTHENIUM CARBONYL(15243-33-1)
• EPA Substance Registry System: RUTHENIUM CARBONYL(15243-33-1)

Safety Data

• Hazard Codes: F,Xn
• Statements: 11-20-2017/11/20
• Safety Statements: 24/25
• RIDADR: 1325
• WGK Germany: 3
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 15243-33-1(Hazardous Substances Data)

Usage

Reactions

Catalyst for the conversion of enynes to catechol derivatives. Catalyst for the intermolecular [2+2+1] cycloaddition of ketones, CO and alkenes or alkynes. 3-Component couplings. Reaction of α,β-unsaturated imines with carbon monoxide and alkenes to form β,γ-unsaturated γ-butyroactams. Ester decarboxylation. Catalyst for hydroamination and C-H bond activation. Used in sp3 C-H bond arylation and carbonylation. Ru/halide catalytic system for C-C bond forming reaction between alkynes and unsaturated carbonyl compounds. Amination of α-hydroxy amides.

Chemical Properties

orange plates

Uses

A H-transfer catalyst. It is used in carbonylation catalysis of the allylic amination of unactivated olefins by nitroarenes, reductive carbonylation of mononitro aromatic compounds to carbamates, and as a catalyst for cycloaddition reactions. It is employed as a precursor for the synthesis of Ru nanoparticles. Catalyst used in the intermolecular [3+2+1] cycloaddition of alpha,beta-unsaturated ketones with silylacetylenes and carbon monoxide, to produce alpha-pyrones. Catalyzes the coupling of silanes with thiols, alcohols and amines with high turnover number (TON) and high turnover frequency (TOF).

General Description

Atomic number of base material: 44 Ruthenium

InChI:InChI=1/12CO.3Ru/c12*1-2;;;

Synthetic route

ruthenium pentacarbonyl (16406-48-7) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In further solvent(s) byproducts: CO; exposure to an N2-atmosphere, hydrocarbon soln.;;	100%
In pentane storing of soln. for 1 day under Ar at room temp.;
In neat (no solvent) decompn. of (Ru(CO)5) at room temp.;;

Ru2[μ-η(2)-OC(CF3)O]2(CO)6 + carbon monoxide (201230-82-2) + cesium trifluoroacetate (21907-50-6) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + fac-Cs[Ru(CF3COO)3(CO)3] (184584-51-8)

Conditions	Yield
In tetrahydrofuran CO-atmosphere; stirring Ru-complex soln. (30°C, 8 h); sepn. of Ru3(CO)12, evapn.;	A 95% B 99%

Ru3{μ-H,μ-O=C(NMe2)}(CO)10 + ethene (74-85-1) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru2(OCC2H5)(OCN(CH3)2)(CO)6

Conditions

Yield

With CO In hexane under N2; Ru compd. is dissolved in hexane, transferred to a Hoke cylinder, charged with CO (1 atm) and ethylene (3 atm), allowed to sit at room temp. for 20 h; gases are vented, IR, mixt. is reduced in volume, cooled to -20°C: crystn. of Ru3(CO)12, soln. is filtered after 12 h, reduced in volume to half, IR, soln. is cooled to -20°C, supernatant liq. is similar worked up; elem. anal.;

A n/a B 98%

K(1+)*RuCl2(CO)2(CO2H)(1-) = K[RuCl2(CO)2(CO2H)] + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In 2-methoxy-ethanol byproducts: CO2, KCl; heating the Ru complex and CO in 2-methoxyethanol to 85°C for 20 min; filtration, washing (EtOH);	97%

diruthenium(II,III) tetraacetatechloride → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With carbon monoxide In methanol; dichloromethane; water High Pressure; dissolving Ru2(CH3COO)4Cl in CH3OH-CH2Cl2-H2O (10:10:1), charging into pressure vessel, pressurizing to 1000 psi with CO, stirring at this pressure for 4 h; venting CO atmosphere, partially removing solvent by vac. distn., pptn.filtration;	96%

H(μ-H)Ru3(CO)11 → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With carbon monoxide In methanol CO atmosphere (room temp., 10 min, stirring), pptn.; redn. of vol. (vac.), filtration off, washing (MeOH): 87.7%; evapn. of filtrate to dryness, chromy. (silica, hexane): 7.9%;	95.7%

[Ru(CO)4(η2-ethylene)] (52621-15-5) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In n-heptane N2-atmosphere; refluxing for 2 h; solvent removal (vac.), TLC (CH2Cl2/hexane=1:1);	95%

tricarbonyldichlororuthenium (II) dimer + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With sodium carbonate In ethylene glycol molar ratio Ru:Na2CO3=1:1; bubbling CO for 5 h at 95°C; extn. of ppt. and sublimate with CH2Cl2 (room temp.), evapn., washing (water);	93%

ethene (74-85-1) + Ru3(H)(OCC6H5)(CO)10 → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru2(OCC2H5)(OCC6H5)(CO)6

Conditions

Yield

With CO In hexane under N2; Ru compd. is dissolved in hexane, transferred to a Hoke cylinder, charged with CO (1 atm) and ethylene (3 atm), allowed to sit at room temp. for 20 h; gases are vented, IR, mixt. is reduced in volume, cooled to -20°C: crystn. of Ru3(CO)12, soln. is filtered after 12 h, reduced in volume to half, IR, soln. is cooled to -20°C, supernatant liq. is similar worked up; elem. anal.;

A n/a B 93%

ruthenium trichloride + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With triethylamine In propan-1-ol; water at 85℃; under 2625.26 Torr; Concentration; Reagent/catalyst; Solvent; Temperature; Pressure; Autoclave;	92.5%
In methanol at 125℃; under 48754.9 Torr; for 8h; Autoclave;
With triethylamine In propan-1-ol at 85℃; under 2625.26 Torr; for 17h; Autoclave; Gas phase;

Ru3(2-)*11CO*2N(P(C6H5)3)2(1+)=(N(P(C6H5)3)2)2(Ru3(CO)11) + tropylium tetrafluoroborate (27081-10-3) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With carbon monoxide In not given dropwise addn. of CO and Ru-cluster soln. (CH2Cl2 or MeCN) to soln. of (C7H7)BF4 (N2 purge, room temp.); IR monitoring;	92%

ruthenium trichloride hydrate + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With sodium carbonate In ethylene glycol bubbling of CO (1 atm) through a soln. of Ru salt in ethylene glycol for5 min, heating under CO at 110°C for 2 h, cooling to 25°C , addn. of Na2CO3 (Na2CO3:Ru mol. ratio 3:2), heating under CO at 80°C for 7 h; extn. of sublimate and reaction mixt. with dichloromethane at room temp., evapn. to dryness, washing the solid with water and then pentane;	91%
With potassium hydroxide In 2-ethoxy-ethanol under CO (1 atm), 1 h at 80°C, 45 min at 135°C, then addedKOH (2 equiv.) at 75°C under CO bubbling;	90%
With Fe or stainless steel or Fe-Cr-alloy In ethanol byproducts: RuO2, [RuCl2(CO)3]2; High Pressure; by a react. of Ru-contg. compd. in EtOH soln. at high CO pressure (50 bar) in autoclave in the presence of Fe plate or stainless steel (76% Fe, 17% Cr, 7% Ni) or Fe-Cr alloy (72.8% Fe, 22% Cr, 5% Al, 0.1% Y, 0.1 Zr);at 125°C; react. time: > 3 h; cooling in an ice bath; solid was filtered off and the resulting soln. was evapd. to dryness;	80%

Ru3(H)(OCC2H5)(CO)10 + ethene (74-85-1) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + {(μ-propionyl)2(carbonyl)6diruthenium}

Conditions

Yield

With CO In hexane under N2; Ru compd. is dissolved in hexane, transferred to a Hoke cylinder, charged with CO (1 atm) and ethylene (3 atm), allowed to sit at room temp. for 20 h; gases are vented, IR, mixt. is reduced in volume, cooled to -20°C: crystn. of Ru3(CO)12, soln. is filtered after 12 h, reduced in volume to half, IR, soln. is cooled to -20°C, supernatant liq. is similar worked up; elem. anal.;

A 27% B 91%

HRu3(CO)10(μ-η2-C(O)CH3) (80800-53-9) + ethene (74-85-1) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru2(OCC2H5)(OCCH3)(CO)6

Conditions

Yield

With CO In hexane under N2; Ru compd. is dissolved in hexane, transferred to a Hoke cylinder, charged with CO (1 atm) and ethylene (3 atm), allowed to sit at room temp. for 20 h; gases are vented, IR, mixt. is reduced in volume, cooled to -20°C: crystn. of Ru3(CO)12, soln. is filtered after 12 h, reduced in volume to half, IR, soln. is cooled to -20°C, supernatant liq. is similar worked up; elem. anal.;

A n/a B 91%

carbon monoxide (201230-82-2) + ruthenium(III)chloride (10049-08-8) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With caesium carbonate In methanol other Radiation; mixt. of RuCl3, Cs2CO3 and MeOH was sealed in microwave app.; CO (50 psi) was introduced; sealed; heated with stirring to 110°C using power of 300 W; held for 10 min; cooled to 50°C; evapd. (vac.); hexane added; heated; solvent removed;	90%
With Cu or Zn In ethanol other Radiation; γ irradiation of 1E-3 mol/l RuCl3 in ethanol under CO atmosphere at room temp. in presence of Cu or Zn powder;
With zinc In methanol heating RuCl3 with Zn at a CO pressure of 5-10 atm at 65 °C for 30 h;; extraction of thr solid residue of the filtration; pptn. on concentrating;;
With Zn In methanol heating RuCl3 with Zn at a CO pressure of 5-10 atm at 65 °C for 30 h;; extraction of thr solid residue of the filtration; pptn. on concentrating;;

[Ru(CO)4(η2-ethylene)] (52621-15-5) + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In n-heptane CO-atmosphere; refluxing for 2 h; TLC (CH2Cl2/hexane=1:1); other unidentified products;	90%

Ru3H(H)(CO)11 → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + H4(ruthenium)4(carbonyl)12 + dihydrotetraruthenium tridecacarbonyl

Conditions	Yield
In dichloromethane-d2 thermal decompn. in soln. at room temp. within 15 min;	A 90% B n/a C n/a

Ru3H(1+)*10CO*SC6H5(1-)=HRu3(CO)10(SC6H5) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + ruthenium3(carbonyl)9(μ3-carbonyl)(μ3-sulfido) (105121-22-0)

Conditions	Yield
With CO In hexane refluxing (30 min, bubbling CO); crystn., solvent removal (vac.), dissoln. in CH2Cl2, thin layer chromy.(SiO2, hexane); elem. anal.;	A n/a B 89%

H3Ru3(μ3-methoxymethylidyne)(carbonyl)9 (71562-47-5) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + ruthenium pentacarbonyl (16406-48-7) + Dimethyl ether (115-10-6)

Conditions

Yield

With carbon monoxide; hydrogen In toluene an autoclave containing a soln. of Ru3-cluster in toluene was pressurized to 500 psig with 1:1 CO-H2 and was heated at 130°C for 23 h; cooled, gases were vented through U-trap (liq. N2), condensate was shown to be Me2O and Ru(CO)5 by mass spectrometry, toluene soln. was filtered (ppt. - Ru3(CO)12 identified by IR data), filtrate evapd., residue chromd. on SiO2 to give addnl. Ru3(CO)12;

A 89% B <1 C n/a

Ru3(CO)10H(OCC6H4N(CH3)2) (140111-19-9) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 4-dimethylamino-benzaldehyde (100-10-7)

Conditions	Yield
With CO In benzene High Pressure; heating (3 bar CO, 90 min, 80°C); chromy. (hexane);	A 88% B 81%

ruthenium(III) chloride trihydrate + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
With KOH In methanol; 2-methoxy-ethanol byproducts: KCl; heating RuCl3*3H2O and CO in 2-methoxyethanol to 125°C for ca. 2 h, after cooling to 20°C addn. of methanolic KOH, heating to 85°C for 20 min; filtration;	86%
In methanol High Pressure; a soln. of RuCl3 in methanol was charged with 2.0 MPa CO and pressurizedto 5.0 MPa, the autoclave was placed in a thermostatic oil bath with st irring for 8 h at 125°C, cooled to room temp.; filtered, recrystd. from toluene;	54%

methanol (67-56-1) + bis(dimethylgermyl)methane ruthenium tetracarbonyl (131145-73-8) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + bis(dimethylmethoxygermyl)methane (131245-48-2)

Conditions	Yield
the Ru complex reacts with an excess of methanol (6 h 80°C); fractional distn.; elem. anal.;	A n/a B 85%

{HRu3(CO)9(μ3-η2:η2:η2-C6H6)}BF4 (128391-81-1) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru3(CO)9(μ3:η(2):η(2):η(2)-C6H6) (128363-71-3)

Conditions	Yield
With 1,8-diazabicyclo{5.4.0}undec-7-ene In dichloromethane (N2); added dropwise a soln. of N-compound to soln. of Ru-complex; filtered; evapd. (vac.); chromy.;	A n/a B 85%

tricarbonyl-cyclo{dicarbonyl(cyclopentadienyl)molybdenum}-μ3-(ethylmethylidine)-μ3-hydrido(tricarbonylcobalt)ruthenium (Co-Mo, Co-Ru, Mo-Ru) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + RuCoMo(CO)8Cp(μ3-C=CHMe)

Conditions	Yield
In toluene byproducts: H2; stirred at 80°C for 1 h; solvent removed under vacuum, chromd. (silica gel, hexane), solvent removed under vacuum from the 2. fraction, crystd. at -30°C;	A n/a B 83%

bis(dimethylgermyl)ethane ruthenium tetracarbonyl (131145-74-9) + Nitrosobenzene (586-96-9) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + (CH3)2GeCH2CH2Ge(CH3)2O (120926-63-8) + Azobenzene (1227476-15-4)

Conditions	Yield
In benzene byproducts: CO; the Ru complex reacts in benzene with C6H5NO in a closed tube at 140°C (48 h);	A n/a B 82% C n/a

Ru4H3(CO)10C6H5PCH2P(C6H5)2 (98976-61-5) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru3(μ-H)(CO)9(μ3-PPhCH2PPh2)

Conditions	Yield
With CO In toluene CO was bubbled through a toluene soln. of complex heated under reflux for 3 h, the soln. was cooled; chromy. on silica gel, eluent heptane-toluene;	A 18.7% B 80.5%

ruthenium(IV) oxide hydrate + carbon monoxide (201230-82-2) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In toluene stainless steel autoclave; pressurizing with 20 atm CO, heating to 160°C for 2 h (stirring); cooling, collection (filtration), washing (cold PhMe);	80%
In further solvent(s) stainless steel autoclave, PhNH2 solvent; pressurizing with 5 atm CO, heating to 160°C for 2 h (stirring); cooling, collection (filtration), washing (cold PhMe);	70%

[Ru3(acetonitrile)2(CO)10] + Triethylsilanol (597-52-4) → dodecacarbonyl-triangulo-triruthenium (15243-33-1)

Conditions	Yield
In acetonitrile N2 atmosphere; stirring (24 h, room temp.);	80%
In neat (no solvent) N2 atmosphere; 70°C;

bis(dimethylgermyl)methane ruthenium tetracarbonyl (131145-73-8) + 2-propynyl chloride (624-65-7) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + bis(chlorodimethylgermyl)methane (98187-50-9)

Conditions	Yield
In benzene HCCCH2Cl reacts with the tetracarbonyl ruthenium complex (80°C, 4 h, inert conditions); identification by spectroscopy;	A n/a B 80%

{Ru4(Se2)(CO)8(CO)3} + bis(diphenylphosphino)acetylene (5112-95-8) → dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ru3Se2(CO)7((C6H5)2PCCP(C6H5)2)

Conditions	Yield
In dichloromethane react. under dry N2 using Schlenk and vac.-line techniques; addn. of 1.0 equiv. of the acetylene to Ru-complex in CH2Cl2 with stirring (orange soln.), react. for 1 h at room temp.; TLC (Kiesegel, eluent CH2Cl2-hexane 2:3), orange band, slow evapn. of a CH2Cl2-hexane soln.; elem. anal.;	A 20% B 80%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + carbon monoxide (201230-82-2) → ruthenium pentacarbonyl (16406-48-7)

Conditions	Yield
In hexane Irradiation (UV/VIS); photolysis (>376nm, filtered 250 W high pressure mercury arc) in n-hexane (ca. 6ml of a 1E-4M soln.) under ca. 600Torr CO for 3h;; monitoring of react. by IR;;	100%
In tetrahydrofuran High Pressure; 80 bar CO, autoclave; 150°C (5 h);	73%
In hexane for 3h; Inert atmosphere; Schlenk technique; UV-irradiation;

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 4,5-diethyl-2,5-dihydro-3-isopropenyl-2,2-dimethyl-1,2,5-selenasilaborole (118734-49-9) → tricarbonyl(η4-4,5-diethyl-2,5-dihydro-3-isopropenyl-2,2-dimethyl-1,2,5-selenasilaborole)ruthenium (118772-38-6) + carbon monoxide (201230-82-2)

Conditions	Yield
In 1,3,5-trimethyl-benzene Ar atmosphere, heating (140°C, 4 h); filtn., solvent removal (0.001 Torr), sublimation (75-80°C, 0.001 Torr); elem. anal.;	A 82% B 100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + trisodium tris(3-sulfophenyl)phosphine (63995-70-0) → 3Na(1+)*Ru3(CO)11(P(C6H4SO3)3)(3-)=Ru3(CO)11(P(C6H4SO3Na)3)

Conditions	Yield
In methanol N2-atmosphere, molar ratio = 1 : 1; refluxing (2 h); evapn. (reduced pressure), washing (hexane), drying (vac.);	100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + trisodium tris(3-sulfophenyl)phosphine (63995-70-0) → 6Na(1+)*Ru3(CO)10(P(C6H4SO3)3)2(6-)=Ru3(CO)10(P(C6H4SO3Na)3)2

Conditions	Yield
In methanol N2-atmosphere, molar ratio = 1 : 2; refluxing (2 h); evapn. (reduced pressure), washing (hexane), drying (vac.);	100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + trisodium tris(3-sulfophenyl)phosphine (63995-70-0) → 9Na(1+)*Ru3(CO)9(P(C6H4SO3)3)3(9-)=Ru3(CO)9(P(C6H4SO3Na)3)3

Conditions	Yield
In methanol N2-atmosphere, molar ratio = 1 : 3; refluxing (2 h); evapn. (reduced pressure), washing (hexane), drying (vac.);	100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + (triphenylphosphine)gold(I) chloride (14243-64-2) + acetonitrile (75-05-8) → Ru3(μ-AuPPh3)(μ-Cl)(CO)10

Conditions	Yield
With (CH3)3NO In dichloromethane; acetonitrile (N2), soln. of Me3NO in CH3CN added dropwise to soln. of Ru complex in CH2Cl2 at -78°C over 15 min, slowly warmed to room temp., reacted for 15 min, treated with Au complex, stirred at room temp. for 1.5 h; evapd.(vac.), elem. anal.;	100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 5,10,15,20-tetrakis(p-tert-butylphenyl)porphyrin (110452-48-7) + acetonitrile (75-05-8) → [acetonitrile][carbonyl][5,10,15,20-tetrakis(4-tertbutylphenyl)porphyrinato]ruthenium(II)

Conditions	Yield
Stage #1: dodecacarbonyl-triangulo-triruthenium; 5,10,15,20-tetrakis(p-tert-butylphenyl)porphyrin In 1,2-dichloro-benzene at 160℃; for 12h; Inert atmosphere; Stage #2: acetonitrile In 1,2-dichloro-benzene at 80℃; for 12h; Inert atmosphere;	100%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + malonic acid (141-82-2) → 2Ru(1+)*4CO*OOCCH2COO(2-)=[Ru2(CO)4(OOCCH2COO)]

Conditions	Yield
In 1,4-dioxane; benzene byproducts: CO; Ru3(CO)12 and malonic acid were refluxed in benzene/dioxane under a slow flow of N2 for 24 h;; the solid was filtered off from the hot suspension, washed with dioxaneand diethyl ether, and dried under vac.; elem. anal.;;	99.4%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) → ruthenium pentacarbonyl (16406-48-7)

Conditions	Yield
With CO In n-heptane 133 atm CO, 100°C, 24 h;	99%
With carbon monoxide In diethylene glycol Irradiation (UV/VIS); 25°C, 1 atm of CO; UV monitoring; not isolated, detected by IR;
With carbon monoxide In octane Irradiation (UV/VIS); 25°C, 1 atm of CO; UV monitoring; not isolated, detected by IR;

pyridine (110-86-1) + dodecacarbonyl-triangulo-triruthenium (15243-33-1) + trifluoroacetic acid (76-05-1) → RuH(CF3CO2)(CO)2(C5H5N)2 (166821-97-2, 167073-80-5)

Conditions	Yield
In pyridine byproducts: CO; 95°C, 10 min; evapn. (reduced pressure), dissoln. in EtOH, Et2O addn., crystn. (0°C); isomer mixt. not sepd.;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) → [1,2-bis(diphenylphosphino)ethane]tricarbonylruthenium (58201-22-2)

Conditions	Yield
With carbon monoxide; 1,2-bis-(diphenylphosphino)ethane In benzene equimolar amts., 100 atm CO, 100°C, 4-5 h; crystn. (< 0°C, 4-5 h), washing (C6H6, light petroleum), drying (vac.); elem. anal.;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + acetonitrile (75-05-8) → Ru3(CO)10(acetonitrile)2 (103257-53-0)

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile Ar-atmosphere; dropwise addn. of slight excess Me3NO to Ru-complex soln.(in CH2Cl2/MeCN=10:1) at -78°C, warming to room temp.; evapn. (reduced pressure); elem. anal.;	99%
With trimethylamine-N-oxide In dichloromethane soln. of Me3NO added to a soln. of Ru-compd. and CH3CN at 0°C about 15 min, stirred for 1 h; filtered about silica gel, evapd.;
In dichloromethane filtration (degassed SiO2), the soln. kept at -10°C;
With (CH3)3NO In dichloromethane

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + sodium (7440-23-5) → sodium tetracarbonylruthenate(II)

Conditions	Yield
In N,N,N,N,N,N-hexamethylphosphoric triamide (Ar); react. metal carbonyl with Na in HMPA for 1 h at 20°C;	99%
In ammonia NH3 (liquid); NH3 distilled onto Na/Ru mixture (acetone/dry ice bath) under vac., slowly warmed to 235 K, vigorously stirred for ca. 60 min, warmed to 260 K; dried (vac., 260 K, 3.5 h);

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + deuterium (16873-17-9) → β-{Ru4D4(CO)12}

Conditions	Yield
In octane byproducts: CO; High Pressure; n-octane added to Ru complex, degassed (vac.), heated at 120°C (bath) under 5 atm (2)H2 for 9 h with intermediate blowings with N2; allowed to cool to room temp. overnight, filtered, dried (vac.);	99%
In not given according to Knox et al., J. Am. Chem. Soc., 97 (1975) 3942; Bruce et al., Inorg. Synth., 26 (1989) 262;

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + succinic acid (110-15-6) → [Ru2(CO)4(butan-1,4-dioato)](n)

Conditions	Yield
In 1,4-dioxane; toluene byproducts: CO; Ru3(CO)12 and succinic acid were refluxed in toluene/dioxane under a slow flow of N2 for 24 h;; the solid was filtered off from the hot suspension, washed with acetoneand diethyl ether, and dried under vac.; elem. anal.;;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + acetonitrile (75-05-8) → Ru3(CO)9(acetonitrile)

Conditions	Yield
With trimethylamine-N-oxide In dichloromethane; acetonitrile Ar-atmosphere; dropwise addn. of excess Me3NO to Ru-complex soln. (in CH2Cl2/MeCN=2:5) at -78°C, warming to room temp.; crystn. on slow removal of solvent (reduced pressure); elem. anal.;	99%

1,4-dihydroxybut-2-yne (110-65-6) + dodecacarbonyl-triangulo-triruthenium (15243-33-1) + bis(triphenylphosphine)iminium chloride (21050-13-5) → [PPN][Ru3(μ-Cl)(μ-HOCH2CCCH2OH)(CO)9]

Conditions	Yield
In tetrahydrofuran Ru3(CO)12 and (PPN)Cl (molar ratio 1:1) dissolved in THF; stirred at room temp. for 3 h under N2 bubbling; monitored by IR spectra; ligand (1 equiv.) added; a few min; evapd.;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 1,2-bis(di(pentafluorophenyl)phosphino)ethane (76858-94-1) → Ru3(CO)10(1,2-bis(bis-pentafluorophenylphosphino)ethane) (225779-93-1, 225779-94-2)

Conditions	Yield
With catalyst:Ph2CO(1-) In tetrahydrofuran catalyst (8 drops) added to THF soln. of Ru compd. (0.078 mmol), ligand (0.086 mmol) added, stirred, catalyst (8-10 drops added), TLC conrol;	99%
With sodium diphenylketyl In tetrahydrofuran under argon, Schlenk setup, 1:2 mixt., heated at 40°C, 5 drops ofsodium diphenylketyl soln. added, stirred (IR control); evapd., dissolved (CH2Cl2), chromd. (silica, C6H12/CH2Cl2), recrystd. (CH2Cl2), elem. anal.;	77%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ph2PC*C-C*CBu(t) (172987-61-0) → [Ru3(CO)11(P(C6H5)2CCCCC(CH3)3)] (163727-43-3)

Conditions	Yield
With sodium benzophenone ketyl In tetrahydrofuran	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + Ph2PC*C-C*CPh (7608-31-3) → [Ru3(CO)11(P(C6H5)2CCCCC6H5)] (163727-44-4)

Conditions	Yield
With sodium benzophenone ketyl In tetrahydrofuran	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + dimethyl(ethoxy)silane (14857-34-2) → [Ru2(CO)8(Si(CH3)2(OC2H5))2]

Conditions	Yield
In hexane Irradiation (UV/VIS); (N2); irradiation (180 W mercury lamp, 25°C, 2 h); prepd. as soln. (spectr. yield);	99%
In hexane Irradiation (UV/VIS); (N2); reflux (1.5 h); concn., TLC (SiO2; CH2Cl2/hexane);	30%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + hydrogen (1333-74-0) → H4(ruthenium)4(carbonyl)12

Conditions	Yield
In octane byproducts: CO; High Pressure; n-octane added to Ru complex, degassed (vac.), heated at 120°C (bath) under 5 atm H2 for 9 h with intermediate blowings with N2; allowed to cool to room temp. overnight, filtered, dried (vac.);	99%

5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (37083-37-7) + dodecacarbonyl-triangulo-triruthenium (15243-33-1) → [Ru(2,6-Cl2tpp)CO] (127390-19-6)

Conditions	Yield
In 1,2,4-trichorobenzene Reflux; Inert atmosphere;	99%

5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (37083-37-7) + dodecacarbonyl-triangulo-triruthenium (15243-33-1) → carbonyl ruthenium(II) 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin (127390-19-6)

Conditions	Yield
In 1,2,4-Trichlorobenzene at 195 - 200℃; Inert atmosphere;	99%
With 1,2,4-Trichlorobenzene at 160 - 165℃; Inert atmosphere;

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + bis[bis(trimethylsilyl)amino]germanium(II) (59863-12-6) → [Ru(Ge(HMDS)2)2(CO)3] (1310738-35-2)

Conditions	Yield
In toluene (N2) Ge(HMDS)2 was added to suspn. (Ru3(CO)12) in toluene and heated at 100°C for 1 h; solvent was removed in vacuo;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 2-(2-methylprop-1-en-1-yl)phenyl formate (1396690-42-8) → 2-oxo-3-isopropyl-2,3-dihydrobenzofuran (4374-68-9)

Conditions	Yield
With 1-(1-phenylethyl)-1H-imidazole In 1,3,5-trimethyl-benzene at 135℃; for 24h; Inert atmosphere; Sealed tube; regioselective reaction;	99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + 2-(cyclopent-1-en-1-yl)phenyl formate (1396690-44-0) → 1,3,3a,9b-tetrahydrocyclopenta[c]chromen-4(2H)-one + spiro-2-one

Conditions	Yield
With 2,4,5-trimethyl-1-phenyl-1H-imidazole In 1,3,5-trimethyl-benzene at 135℃; for 24h; Inert atmosphere; Sealed tube; Overall yield = 75 %; regioselective reaction;	A n/a B 99%

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + C29H48P2 (1620470-32-7) → C31H48O2P2Ru

Conditions	Yield
In tetrahydrofuran for 20h; Inert atmosphere; Reflux;	99%

Upstream product

• 14898-67-0 ruthenium(III) chloride trihydrate 
• 201230-82-2 carbon monoxide 
• 17685-52-8 triiron dodecarbonyl 
• 31378-26-4 tris(2,4-pentanedionato)ruthenium(III) 
• 1333-74-0 hydrogen 
• 42516-72-3 (η6-1,3,5-cyclooctatriene)(η4-1,5-cyclooctadiene)ruthenium(0) 
• 27081-10-3 tropylium tetrafluoroborate 
• 597-52-4 Triethylsilanol 
• 791-31-1 triphenylhydroxysilane 
• 22941-55-5 [ruthenium(II)chloride(carbonyl)3(THF)] 
• 71562-47-5 H3Ru3(μ3-methoxymethylidyne)(carbonyl)9 

Downstream Products

• 64364-79-0 Ru3(CO)10(μ-bis(diphenylphosphino)methane) 
• 86277-00-1 (Ru₃(CO)11)2((C₆H₅)2PCH₂P(C₆H₅)2) 
• 91742-09-5 Ru₂(CO)4(C₆H₅COO)2(C₆H₅COOH)2 
• 86276-97-3 Ru₃(CO)11(cyclohexyl isocyanide) 
• 97150-52-2 {bis(triphenylphosphine)nitrogen}2{Ru₃(CO)11} 
• 71936-70-4 N(P(C₆H₅)3)2⁽¹⁺⁾*Ru₃H(CO)11^(1-)=N(P(C₆H₅)3)2[Ru₃H(CO)11] 

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Relevant articles and documents

Synthesis and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurials

Reaction of the activated cluster [Os3(CO)10(NCMe)2] with [PhHgS(C5H4N)] afforded two new Os-Hg clusters cis-[Os(CO)4{Os3(CO)10(μ-η 2-SC5H4N)(μ-Hg)}2] 1 and [{Os3(CO)10(μ-η2-SC5H 4N)}2(μ4-Hg)] 2 in 25 and 30% yields, respectively. Cluster 1 consists of two {Os3(CO)10(μ-η2-SC5H 4N)(μ-Hg)} subunits bonded to a central Os(CO)4 moiety in a cis configuration. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. Treatment of the same organomercurial with [Ru3(CO)10(NCMe)2] produced the cluster compound cis-[Ru(CO)4{Ru3(CO)9(μ-η 3-SC5H4N)(μ-Hg)}2] 3 (48%). This has a metal skeleton similar to that of 2 with the {S(C5H4N)} ligand moiety bonding to the ruthenium atoms in a μ-η3 fashion. Treatment of [Os3(CO)10(NCMe)2] with [PhHg(mbt)] (Hmbt = 2-mercaptobenzothiazole) afforded [{Os3(CO)10(μ-η2-mbt)} 2(μ4-Hg)] 4 (35%) and [Os3(CO)10(μ-η2-mbt)(μ-η 2-Hg(mbt)] 5 (20%). Cluster 4 is very similar to 2, but the S(C5H4N) ligand is replaced by the mbt ligand, while 5 consists of an Os3 triangle having one edge spanned by both [μ-η2-mbt] and [μ-η2-Hg(mbt)] moieties. The reaction of [Os5C(CO)15] and [Ru3(CO)12] with another class of organomercurial (diphenylthiocarbazono)phenylmercury reagent [PhHgL′] [L′ = SC(N=NPh)(=NNHPh)] containing a N=N functionality under thermal conditions produced [{Os5C(CO)14(μ-η2-SPh)} 2(μ4-Hg)] 6 (26%) and [{Os5C(CO)14(μ-η2-L′)} 2(μ4-Hg)] 7 (34%) and [Ru2(CO)4Ph{μ-η2-C(O)Ph}(μ 2-S)(μ-η2-L′)] 8 (15%), [Ru2(CO)4(C(O)Ph) {μ-η2-C(O)Ph}(μ2-S)(μ-η 2-L′)] 9 (15%) and [{Ru(CO)2Ph}2(μ-η2-L′)] 10 (45%), respectively. In clusters 6 and 7, two {Os5C(CO)14} subunits linked by a common wingtip mercury atom, are bonded with both μ-η2-SPh in 6 and μ-η2-L′ in 7. However, in the case of complexes 8, 9 and 10, only binuclear ruthenium carbonyl complexes formed instead of the expected formation of mixed-metal clusters. Complexes 1-10 result from the cleavage of both Hg-C and Hg-S bonds in the parent organomercury species. All these complexes have been fully characterized by both spectroscopic and crystallographic techniques.

Organosulphur-Transition-metal Chemistry. Part 5. Face Bonding of Cycloheptatrienyl and Cyclo-octatetraene Ligands in Sulphur-Ruthenium Clusters: Crystal and Molecular Structure of t)(μ3-(η7-C7H7))>

The sulphur-ruthenium cluster complex t)> reacts with cycloheptatriene in boiling heptane to give t)(μ3-(η7-C7H7))> and t)(μ-(η7-C7H7))>.The former contains a facebridging cycloheptatrienyl ligand, established through an X-ray diffraction study.Crystals are monoclinic, space group C2/c, with eight molecules in a unit cell of dimensions a=14.875(6), b=8.902(6), c=30.977(2) Angstroem, and β=94.785(4) deg.The structure has been solved by conventional techniques, revealing the ruthenium atoms to be present in isosceles triangular units disordered in ca. 2:1 ratio via a 60 deg rotation in the ruthenium plane.Refinement was by least squares for 3860 data to R 0.041.The ruthenium triangle is bridged on one side by a μ3-SBut ligand and on the other by a face-bonded C7H7 ring which is planar and lies parallel to the face at a distance of 2.07 Angstroem.The hydrogens of the C7H7 ligand are inclined away from the metal triangle as a result of ?-orbital reorientation.The ruthenium-carbon (ring) distances are compatible with bonding of the C7H7 ligand in η2,η2,η3 fashion to the metal triangle, each atom of which bears two terminal carbonyl groups, but n.m.r. spectra show that the ring rotates freely relative to the face in solution.The high-fild 13C n.m.r. shift (38.7 p.p.m.) for the μ3-(η7-C7H7) ligand is characteristic, comparing with 61.0 p.p.m. for similarly fluxional μ-(η7-C7H7) in t)(μ-(η7-C7H7))>.Treating t)(μ3-(η7-(C7H7))> with CO results in cluster fragmentation to yield t)(μ-(η7-C7H7))>, a reaction attributed to the ability of both SBut and C7H7 ligands to vary their mode of co-ordination.Reactions of t)> with cyclo-octatetraene, cyclo-octatriene, and cyclopentadiene also effect cluster breakdown, forming t)(μ-(η7-C8H9))> or t)(η-C5H5)2>.The sulphur-ruthenium cluster in is less easily destroyed.The reaction with cyclo-octatetrane provides 8-C8H8))>, containing rare face-bonded fluxional C8H8, while with cycloheptatriene the complexes 5-C7H9)(μ3-(η7-C7H7))>, 5-C7H9)(μ3-(η7-C7H7))>, and 7-C7H7))2> are obtained, partly characterised using the 13C n.m.r. criterion of the C7H7 bonding mode.

(13)C NMR study of reorientational dynamics in Ru3(Co)9(μ(3)-Co)(μ(3)-NPh). Relaxation time analysis in the non-motional narrowing regime

The NMR (13)C spin-lattice relaxation times of the phenyl group and equatorial carbonyl carbons in Ru3(CO)9(μ(3)-CO)(μ(3)-NPh) were measured as a function of temperature and resonance frequency in the solvent methylene chloride, and at several temperatures in chloroform. Phenyl T(1)s were used to calculate the diffusion coefficients characterizing molecular tumbling, D(.perp.), and spinning of the phenyl group, D(s); carbonyl relaxation times yielded the parallel diffusion coefficient, D(.paral.). Values of D(.perp.) calculated using the standard motional narrowing assumption were incorrectly observed to be frequency dependent, and inmarked error (by as much as a factor of two) from results obtained usin g the non-motionally narrowed equations. The spinning diffusion coefficients, D(s), were an order of magnitude greater than either D(.perp.) or D(.paral.), but somewhat lower than the rate of the equivalent rotation of free benzene in the same solvents, indicating the existence of a barrier to internal rotation of the phenyl group. Fenske-Hall and extended Hueckel calculations revealed that the barrier arises primarily from steric interactions between the ortho protons of the phenyl group and the carbon atom of the equatorial carbonyls.

The Reduction of (μ2-NO) in 2-NO)> to (μ3-NH) and (μ2-NH2) by Molecular Hydrogen

- reacts with NOBF4 in moist MeCN to generate HRu3(CO)10NO, HRu3(CO)10NH2, and HRu4N(CO)12; the same products, together with H2Ru3(CO)9NH and H4Ru4(CO)12, are observed in the direct hydrogenation of HRu3(CO)10NO.

PROTONATION OF (μ-H)3Ru(μ3-CR)(CO)9. EVIDENCE FOR THE FORMATION OF AN AGOSTIC METAL-HYDROGEN-CARBON BOND

Protonation of (μ-H)3(μ3-CR)(CO)9 (M = Ru, R = Et or M = Os, R = Me) by dissolution in HSO3CF3 yields H3M3(HCR((CO)9+, containing a M-H-C bridge.The products were characterized by 1H and 13C NMR spectroscopy.Decompositions of other protoned methylidyne clusters form CH3R and a variety of metal-containing products.

The Chemical Activation of Iron, Ruthenium, and Osmium Carbonyl Cluster Anion-susing Oxidative Addition

The chemical activation of iron, ruthenium, and osmium carbonyl cluster anions has been achived by investigating their oxidative electrochemistry and then matching the observed electrochemical oxidation potential with chemical reagents, by the use of oxidative addition in the presence of the required ligand; the dianionic clusters (2-), Ru3(CO)11>(2-), (2-), (2-), (2-), and (2-) have been found to react with multi-electron donor ligands in the presence of a suitable oxidant.

Improved Synthesis of the Hexanuclear Clusters (2-), (1-), and H2Ru6(CO)18. The X-Ray Analysis of (1-), a Polynuclear Carbonyl containing an Interstitial Hydrogen Ligand

The X-ray analyses of two crystalline modifications, (I) and (II), of are reported, together with improved synthetic routes to this and the related clusters (2-) and H2Ru6(CO)18.Crystals of (I) are triclinic, space group P1-, with a=18.083(4), b=19.101(4), c=19.238(5) Angstroem, α=117.70(4), β=78.13(2), γ=97.05(2) deg, and Z=4.Crystals of (II) are monoclinic, space group P21/n, with a=33.82(8) b=52.55(10), c=9.832(2) Angstroem, β=92.66(2) deg, and Z=12.Least square refinement using diffractometer data (Mo-Kα) has given an R of 0.0681 for 9165 reflections for (I) and an R of 0.23 (Ru only) for 1485 reflections for (II).The unit cell in (I) contains two independent molecules of (1-), cluster (1) which is ordered and cluster (2) which is disordered between two sites (2A) and (2B) that are related by a non-crystallographic two-fold axis.The combined evidence of the X-ray analyses, 1H n.m.r. studies, i.r. spectra, and variable-temperature 13C n.m.r. is only consistent with the hydrogen ligand lying inside the Ru6 octahedron.

Novel polymeric carbonylhaloruthenium(I) polyanions: Rational design and self-reorganization in the presence of CO2 and H2O

We just need to mix [Ru(CO)3Cl2(thf)] with methanolic NEt4OH - nature will do the rest: The unsaturated fragments thus generated spontaneously polymerize with production of CO2 and H2O, which combine

ROLE OF THE CATION IN THE REACTION OF Ci(CO)4- WITH RuCl3*xH2O. SYNTHESIS AND MOLECULAR STRUCTURE OF THE RUTHENIUM CLUSTER 2

Reaction of with RuCl3 * xH2O (4/1 ratio) in THF affords Ru3(CO)12, , and 2.The latter has been fully characterized by an X-ray structural analysis.These results are compared

Dimethyl sulfide substituted mixed-metal clusters. Synthesis, structure, and characterization of HRuCo3(CO)11(SMe2) and [HRuRh3(CO)9]2[SMe2]3

Ligand substitution reactions of dimethyl sulfide with mixed-metal clusters are described. The clusters HRuCo3(CO)11(SMe2) (1) and [HRuRh3(CO)9]2[SMe2]3 (2) have been prepared by reactions of SMe2 with the neutral parent clusters. Their crystal structures have been established. Dimethyl sulfide coordinates terminally as a two-electron donor on basal cobalt in 1 and as a bridging four-electron donor causing unusual dimerization of clusters in 2. The carbonyl arrangement of the parent clusters was not changed during the ligand substitution, and hydride ligands bridge the three basal metals in both compounds.

New insight into a convenient base-promoted synthesis of Ru3(CO)12

The addition of two equivalents of KOH per Ru under 1 atm CO at 75°C to a mixture of [Ru(CO)2Cl2]n and [Ru-(CO)3Cl2]2 generated in situ by carbonylation of 5 grams of RuCl3·3H2O in 2-ethoxyethanol, triggers a reaction cascade producing Ru3(CO)12 in yields exceeding 90% within 45 minutes.

Cluster chemistry. 27. The synthesis and structural characterization of three mixed gold-cobalt-ruthenium carbonyl clusters Ph3PAuCoRu3(CO)13, (Ph3PAu)2CoRu3(H)(CO)12, and (Ph3PAu)3CoRu3(CO)12

A unique series of mixed gold-cobalt-ruthenium carbonyl clusters has been prepared and structurally characterized. Reaction of [(Ph3PAu)3O]BF4 with HCoRu3(CO)13 gives the three clusters Ph3PAu-CoRu3(CO)13 (1), (Ph3PAu)2CoRu3(H)(CO)12 (2), and (Ph3PAu)3CoRu3(CO)12 (3). An alternative specific route to 3 is via [(Ph3PAu)3O]BF4 and [CoRu3(CO)13] , while Ph3PAuCl and [CoRu3(CO)13]- give exclusively 1. For 1 [C31H15O13AuCoPRu3, a = 9.345 (3) ?, b = 14.217 (4) ?, c = 14.721 (3) ?, α = 114.83 (2)°, β = 93.16 (2)° γ = 92.44°, triclinic, P1, Z = 2] a trigonal-bipyramidal core is found, with the Ph3PAu group triply bridging a CoRu2 triangle. For 2 [C48H31Au2CoO12P2Ru 3·0.5CH2Cl2, a = 35.173 (9) ?, b = 13.548 (9) ?, c = 23.193 (4) ?, β = 102.27 (2)°, monoclinic, C2/c, Z = 8] a capped trigonal-bipyramid core exists with the second Ph3PAu group capping an AuRu2 face of 1 and the hydride ligand bridging an Ru-Ru bond. The structures are rationalized in terms of the maximum number of face-sharing tetrahedra; the isolobality of H and Ph3PAu is not valid in the context of polygold clusters.

METAL CLUSTERS IN CATALYSIS. THE REACTIVITY OF ALKYNE- AND VINYLIDENE-SUBSTITUTED HOMO- AND HETERO-METALLIC CLUSTERS TOWARDS MOLECULAR HYDROGEN IN HOMOGENEOUS CONDITIONS

The reactivity of alkyne- and vinylidene-substituted clusters towards molecular hydrogen in homogeneous conditions has been studied by means of GC and GC/MS techniques.The reactivity of the homo- and hetero-metallic cluster frames (containing nickel and one of the iron triad metals) is discussed, as well as that of the coordinated ligands.Under hydrogen the cluster cores are modified, sometimes as a part of a catalytic cycle.The products obtainable from the coordinated small molecules seem to depend mainly on the overall electronic situation of the clusters or on the C-C distances in the alkynes, and to a lesser extent on the number of coordinating metal centres.In some instances it was observed that when both free alkynes and substituted clusters were present, only the coordinated alkynes were hydrogenated.

The use of photogenerated intermediates in the study of cluster build-up reactions: The generation of Ru6C(CO)17 from Ru3(CO)12

The use of photochemistry in the study of cluster build-up reactions involving transition-metal carbonyl complexes has been illustrated by an investigation into the generation of the hexanuclear carbido cluster Ru6C(CO)17 from the tr

Tri- and tetranuclear mixed-metal clusters containing alkyne ligands: Synthesis and structure of [Ru3Ir(CO)11(RCCR')]-, Rru2Ir(CO)9(RCCR')]-, and [HRu2Ir(CO)9(RCCR')]

The tetrahedral cluster anion [Ru3Ir(CO)13]- (1) reacts with internal alkynes RC≡CR' to afford the alkyne derivatives [Ru3Ir(CO)11(RCCR')]- (2: R = R' = Ph; 3: R = R' = Et; 4: R = Ph; R' = Me; 5: R = R' = Me) which have a butterfly arrangement of the Ru3Ir skeleton in which the alkyne is coordinated in a μ4-η2 fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions [Ru2Ir(CO)9(RCCR')]- (6: R = R' = Ph; 7: R = R' = Et; 8: R = Ph; R' = Me; 9: R = R' = Me), in which the alkyne ligand is coordinated in a μ3-η2 parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydrido clusters [HRu2Ir(CO)9(RC≡CR')] (10: R = R' = Ph; 11: R = R' = Et; 12: R = Ph; R' = Me; 13: R = R' = Me). The protonation of the butterfly anions 2 and 3, however, gives rise to the formation of the neutral tetrahedral clusters [HRu3Ir(CO)11(RCCR')] (14: R = R' = Ph and 15: R = R' = Et), respectively. The analogous clusters [HRu3Ir(CO)11(PhCCCH3)] (16) and [HRu3Ir(CO)11(CH3CCCH3)] (17) are only accessible from the reaction of the neutral cluster [HRu3Ir(CO)13] with the corresponding alkynes. The complexes 2, 4, 5, 6, 10, 12 and 15 are characterised by X-ray structure analysis.

The synthesis of heteronuclear clusters containing cyclopentadienyl- or pentamethylcyclopentadienyliridium and ruthenium or osmium

The reaction of Cp*Ir(CO)2 or CpIr(CO)2 with Ru3(CO)12 under a hydrogen atmosphere afforded the heterometallic clusters Cp*IrRu3(μ-H)2(CO) 10 and CpIrRu3(μ-H)2(CO)10, respectively, in moderate yields. In the former reaction, the tetrahydrido cluster Cp*IrRu3(μ-H)4(CO)9 was also formed in trace amounts, although this cluster can be obtained in high yields by the hydrogenation of Cp*IrRu3(μ-H)2(CO) 10; the Cp analogue was not obtainable. The reaction of Os 3(μ-H)2(CO)10 with Cp*Ir(CO) 2 afforded the osmium analogue Cp*IrOs3(μ-H) 2(CO)10 in 70% yield, along with a trace amount of the pentanuclear cluster Cp*IrOs4(μ-H)2(CO) 13. Hydrogenation of Cp*IrOs3(μ-H) 2(CO)10 afforded Cp*IrOs3(μ-H) 4(CO)9 in excellent yield. The reaction of Cp*Ir(CO)2 with Os3(CO)10(CH 3CN)2 afforded the known trinuclear cluster Cp*IrOs2(CO)9 and the novel cluster Cp*IrOs3(CO)11. Solution-state NMR studies show that the hydrides in the iridium-ruthenium clusters are highly fluxional even at low temperatures while those in the iridium-osmium clusters are less so.

Formation of H2Ru6(CO)17 from H2Ru6(CO)18 an improved synthesis of HRu6(CO)17 B

Spontaneous decarbonylation of the octahedral cluster H2Ru6(CO)18 produces the bicapped tetrahedral cluster H2Ru6(CO)17. The clusters H2Ru6(CO)18 and H2R6(CO)17 have strikingly similar IR and 1 H NMR spectra. In appearance they are indistinguishable; both are deep purple in color. The decarbonylation reaction is partially reversible under low pressures of CO. Reaction of H2Ru6(CO)17 with BH3S(CH3)2 provides an improved synthesis of HRu6(CO)17B, an octahedral cluster with a boron atom at the center of the Ru6 core. HRu6(CO)17B reacts with excess CO at high pressures to produce HRu4(CO)12BH2 and ruthenaboride clusters with pentanuclear metal cores that are proposed to be HRu5(CO)15B and HRu5(CO)16B.

Synthesis and Structural Characterisation of the Hexanuclear, Bimetallic, Ladder-like Cluster HRu5Cu(CO)18PPh3

The bimetallic cluster HRu5Cu(CO)18PPh3 has been prepared by the reaction of CO with H3Ru4(CO)12CuPPh3, characterised by X-ray crystal structure analysis, and shown to contain a 'ladder-like' arrangement of Ru5Cu based on triangular units.

Ligand substitutions in Ru-Pt clusters: Isolation of compounds with unusual geometries

Ligand substitution reactions of the COD (1,5-cyclooctadiene) ligand for CO or phosphines in the clusters [Ru5C(CO)14Pt(COD)] (1) and [Ru6C(CO)16Pt(COD)] (2) were investigated. Reactions with carbon monoxide gave selectively [Ru5CPt(CO)16] (3) from 1, but led to loss of either a ruthenium or the Pt(COD) unit from the Ru6Pt cluster (2). Substitution of the COD ligand by PPh3 in 1 gave [Ru5C(CO)14Pt(PPh3)2] (8) selectively, while with dppm the main product of the reaction was [Ru5C(CO)14Pt(μ-dppm)] (10). On the other hand, the reactions involving [Ru6C(CO)16Pt(COD)] (2) and phosphines led mainly to extrusion of the Pt(COD) fragment and formation of Ru-only derivatives. More precisely, with triphenylphosphine, the two clusters [Ru6C(CO)16PPh3] (16) and [Ru6C(CO)15(PPh3)2] (18) were obtained from 2, while with dppm, the compounds [Ru6C(CO)15(dppm)] (15) and [Ru6C(CO)13(dppm)2] (19) were formed. In the latter case, two additional products of increased nuclearity were isolated: [Ru6C(CO)15Pt2(dppm)] (20) and [Ru6C(CO)16Pt3(dppm)2] (21). All the compounds described were characterised by spectroscopic methods and the structures of the new species were determined by X-ray crystallography.

Reactivity of the 1-azavinylidene cluster [Ru3(μ-H)(μ-N=CPh2)(CO)10] with hydrogen, tertiary silanes and tertiary stannanes

The reactivity of the 1-azavinylidene cluster [Ru3(μ-H)(μ-N=CPh2)(CO)10] (1) with hydrogen, tertiary silanes and tertiary stannanes has been investigated. The reaction of 1 with hydrogen (1 atm, 110°C) gives [Ru4/sub

Reproducible high-yield syntheses of [Ru3(CO)12], [H4Ru4(CO)12], and [Ru6C(CO)16]2- by a convenient two-step methodology involving controlled reduction in ethylene glycol of RuCl3·nH2O

Ru3CO12 [H4Ru4(CO)12], and [Ru6C(CO)16]2- have been synthesized in reproducible high yields and under mild conditions (1 atm) by a two-step methodology involving (i) first carbonylation of RuCl3·nH2O dissolved in ethylene glycol to give a mixture of tri- and di-carbonyl ruthenium(II) species, probably of the kind [Ru(CO)3Cl2(ethylene glycol)] and [Ru(CO)2Cl2(ethylene glycol)x ] (x = 1, 2), and (ii) addition of specific amounts of alkali carbonates and further reductive carbonylation to give the desired ruthenium carbonyl cluster. The selectivity of the second step is controlled by the: (i) nature and quantity of the alkali carbonate (Na2CO3 or K2CO3); (ii) gas-phase composition (CO or CO+H2); (iii) temperature.

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.

Water-Soluble Ruthenium(II) Carbonyls with 1,3,5-Triaza-7-phosphoadamantane

As a continuation of our strategy for preparing new Ru(II) precursors with improved water solubility through the introduction of highly water-soluble 1,3,5-triaza-7-phosphoadamantane (PTA) supporting ligands in the coordination sphere, in this work, we address the largely unexplored preparation of Ru(II)-PTA carbonyls. Two complementary synthetic approaches were used: (1) the treatment of a series of neutral Ru(II)-CO-dmso compounds of general formula RuCl2(CO)n(dmso)4-n (n = 1-3, 1-5) with PTA; (2) the reaction of Ru(II)-PTA complexes with CO. Through the first approach, we obtained and fully characterized seven novel neutral compounds bearing from one to three PTA ligands per Ru atom, namely, the four monocarbonyls, cis,cis,trans-RuCl2(CO)(dmso-S)(PTA)2 (6), trans-RuCl2(CO)(PTA)3 (7), cis,mer-RuCl2(CO)(PTA)3 (8), and trans,trans,trans-RuCl2(CO)(OH2)(PTA)2 (10), and the three dicarbonyls, trans,trans,trans-RuCl2(CO)2(PTA)2 (11), [RuCl2(CO)2(PTA)]2 (12), and cis,cis,trans-RuCl2(CO)2(PTA)2 (13). The less stable, and thus more elusive, species fac-RuCl2(CO)(PTA)3 (9) and cis,cis,cis-RuCl2(CO)2(PTA)2 (14) were also unambiguously identified but could not be obtained in pure form and fully characterized. The complementary synthetic approach, that involved the treatment of the trans- and cis-RuCl2(PTA)4 (15, 16) isomers with CO, afforded only one new Ru(II)-PTA carbonyl, the cationic species cis-[RuCl(CO)(PTA)4]Cl (17). In general, the choice of the solvent was very relevant for obtaining the products with high yield and purity. We were unable to isolate Ru(II)-PTA compounds with more than two carbonyls. The thermodynamically preferred species have CO trans to Cl and two mutually trans PTAs, and only in the dinuclear compound 12 there is a single PTA per Ru atom. Compounds 7 and 17 feature the unprecedented trans-{Ru(CO)(PTA)} fragment. The X-ray structures of cis,cis,cis-RuCl2(CO)2(dmso)2 (3), 6-8, 10, 11, 13, and 17 are also reported. All compounds are new, are air-stable, and show a good solubility in water (S from 10 to 165 g·L-1) and, most often, also in chloroform.