Carbon monoxide with MeOH

Carbon monoxide in MeOH reacts with LiAlH ... 

Since the 1970s, palladium and platinum complexes with dibenzylideneacetone Pd(dba)2 and M2(dba)3 (M = Pd, Pt) have been known to react under mild conditions with either hydrogen or carbon monoxide, with the formation of a metal [211]. Indeed, there exists a long series of examples where CO and H2 have been used to decompose organometallic precursor molecules [173-177,179-181,183,184,186-188, 212-216]. As an example, the decomposition Ru(COD)(COT) (COD = cyclo-octadiene COT =cydo-octatriene) in an atmosphere of hydrogen is worthy of mention [189,190]. (Scheme 3.20). In this case, the precursor molecule is dissolved in a methanol-THF mixture and is contacted with H2 (3 bar pressure) at room temperature for at least 45 min. Depending on the nature of the MeOH-THF mixture, the Ru particle size can be designed between 3 and 86 nm. 

In this latter case, the role played by Cl could also be coMered by a base 1 i ke pyr i di ne. Model reactions with well de-fined nitrene complexes are needed in order to help the understanding o-f these co-operative ef-feC ts. As a matter o-f -facts, the reaction o-f Ru3carbon monoxide in MeOH/toluene <2 23), gave only aniline, as did the same reaction conducted in the absence o-f Ij2293. 

Cyclic alkynyl carbonates undergo carbonylation in the presence of a palladium catalyst and carbon monoxide (5 MPa) in MeOH to give allenic carboxylates (Eq. 9.118) [92], Bu3P proved superior to Ph3P as the catalyst ligand. An enynyl cyclic carbonate underwent double vicinal carbonylation at 80 °C to produce a five-membered lactone product in 52% yield (Eq. 9.119). When the reaction was performed at 50 °C, the bicyclic enone lactone was produced in 75% yield along with 10% of the y-lactone. 

The binuclear hydride salts are air sensitive, soluble in THF, acetone, CH3CN, MeOH, and diethyl ether, and insoluble in hydrocarbon solvents. They can be stored cold under an inert gas or in vacuo for several months. The salts tend to slowly decompose into W(CO)6 and [PPN] [FeH(CO)4], Carbon monoxide rapidly (within minutes) degrades the dimer into the same products.5 The salts react rapidly with CH3COOD or stronger deuterated acids to form the H-D exchanged products, [FeCrD(CO)9]. The hydrides also act as catalysts in olefin isomerization.10... 

Bis(diphenylphosphino)pyridine forms tetranuclear 111 (L = CO, S02) (83JA6332), and the carbonyl complex on interaction with carbon monoxide and ammonium hexafluorophosphate in chloroform produces [Rh2(g-L)2(CO)2(MeOH)Cl](PF6) (83JA6986). [RhAu(g-L)2](BF4)(N03)... 

RhCl(CO)2]2 (1940 mg, 10 mmol) in benzene (10 mL) at room temperature under nitrogen. Evolution of carbon monoxide was observed, with the formation of a yellow precipitate. After 1 h the reaction mixture was concentrated in vacuo at room temperature. The resulting yellow solid dissolved in MeOH (25 mL) was cooled very slowly to 0 °C. The large yellow prism formed was dried in vacuo to afford... 

Mixed Ruthenium-tii) and -(m) Complexes.—Interactions of the oxo-centred RuI 1 acetate [Ru30(C02Me)6(Me0H)3]+ and the reduced species [Ru30(C02Me)6 (MeOH)3] with carbon monoxide, sulphur dioxide, and NO have been studied.71 Scheme 5 summarizes the products obtained from the latter mixed-valency complex following carbonylation. Only a monocarbonyl complex is seen to be formed, and the... 

A mixture of Pd2(dba)3 and dppp (5 and 20mol% respectively) was dissolved in benzene (1 mL), and the solution was stirred under argon at room temperature for a few minutes. Then a benzene solution (1 mL) of the carbonate 109 (0.5 mmol) and MeOH(l mL) were added, and a rubber balloon filled with with carbon monoxide was attached. The mixture was heated at 50-60 °C for 6h. The reaction mixture was passed through Florisil using... 

The activity of supported Pt catalysts for methanol synthesis from C0-H2 is considerably enhanced when the metal is supported on oxides which exhibit themselves appreciable activity for MeOH synthesis. Furthermore it is found that the rate of methanol formation on Pt-supported catalyst is increased when Th02, Ce02 were mechanically mixed with the Pt catalyst. Such behaviour is typical for bifunctional catalysts. It has already been reported that Th02, Ce02 adsorb carbon monoxide without dissociation. Such activated CO can be hydrogenated to form a formyl species, the formyl species interacting with lattice oxygen will produce a formate intermediate. 

Previous syntheses of this compound often gave low yields from the reaction of OsO with carbon monoxide in the gas phase or by the reaction of OSO4 with carbon monoxide in xylene under hi pressure (128 atm) and temperatures (175 °C). Improved synthesis of this cluster was obtained by the use of OSO4 in MeOH under carbon monoxide pressure, with the white oxycarbonyl 0s404(C0)i2 as a side product We now describe an improved low-pressure synthesis of Os3(CO)i2 from OSO4 in EtOH in very high yield. Caution. Metal carbonyls are toxic and should be handled in a well-ventilated fume hood. 

PdCl2(CO)2] is obtained by reaction of PdCl2 suspended in MeOH or SOGI2 with carbon monoxide.[Pd2Cl4(CO)2] is prepared from [PdCl4] and CO in concentrated (Figure 2.25). Various polynuclear cluster... 

The first total syntheses of grossularines-1 (99a, Scheme 19) and grossularines-2 (99b) were achieved by Hibino. " In these total syntheses, the key compound is triflate 103, which was reacted with carbon monoxide in the presence of MeOH to give ester 104 in... 

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