Geometrical isomers of stibinous and stibinic propenyl compounds

Nesmeyanov, A. N.; Borisov, A. E.; Новикова, Н. В.

doi:10.1016/s0040-4039(01)82706-4

Cited by 9 publications

(2 citation statements)

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“…The dialkenyl-and dialkylmercury compounds used as intermediates were prepared by disproportionation of their respective organomercuric chloride by method described by Nesmeyanov and coworkers. 13 Typically, the alkyl-and alkenylmercuric chlorides were prepared from their respective Grignard reagent and mercuric chloride.14 All organomercury derivatives were purified by high vacuum distillations with subsequent handling performed in a sodium-potassium scavenged inert atmosphere box.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular metal-double bond interactions. VI. Metal-.pi.-electron interactions observed in trialkenylaluminum and -gallium derivatives

Dolzine¹,

Oliver²

1974

J. Am. Chem. Soc.

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Reduction of (OC)gCo3CCO+PF6~with Triethylsilane. (a) In the Absence of Aluminum Chloride. The acylium hexafiuorophosphate prepared from 2.0 mmol of (OC)9Co3CC02Et was slurried in 20 ml of dichloromethane under nitrogen, and 0.80 g (6.6 mmol) of triethylsilane (PCR Inc.) was added. The mixture was stirred at room temperature for 1 hr; a homogeneous solution resulted.The reaction mixture was evaporated under reduced pressure and the residue was extracted with hexane. The red extracts were filtered through a layer of silicic acid and evaporated. The red solid residue was sublimed in vacuo at 50°to give 0.65 g of red solid, melting in the range 95-115°with decomposition. Its ir spectrum suggested that a mixture of CH3CCo3(CO)9 and HCCo3(CO)9 was present (bands at 2960 w, 2920 m, 2880 m, 2820 m, 1160 m, 1000 s, and 855 m cm-1). The entire sample was dissolved in deuteriochloroform and the nmr spectrum which was taken showed that these two products were present in 1 to 1.44 ratio (30 and 43% yields, based on the 0.65 g isolated), respectively, by integration of the resonances at 6 3.76 and 12.10 ppm.(b) In the Presence of Aluminum Chloride. The acylium hexafluorophosphate was prepared from 2.0 mmol of (OC)9Co3CC02-Et and slurried in 15 ml of dichloromethane under nitrogen. To this mixture was added 0.75 g (6.0 mmol) of aluminum chloride. A brief evolution of gas commenced but subsided quickly. Addition of 0.70 g (6.0 mmol) of triethylsilane followed. A brief evolution of gas again was observed and the solution turned from brown to red-brown. Tic (benzene) showed the presence of a single brown material in the solution. After it had been stirred for 10 min at room temperature, the mixture was treated with 150 ml of 15% aqueous HC1 and extracted with 100 ml of dichloromethane.The organic layer was dried and evaporated. The brown solid which remained was taken up in benzene. This solution was passed through a layer of silicic acid and evaporated. The residue was recrystallized from hexane to give 0.68 g (74%) of black needles which decomposed without melting around 115°and whose ir spectrum was identical with that of an authentic sample11 of the aldehyde, (OC)9Co3CCHO.An experiment in which only 2 mmol of aluminum chloride was added to the acylium hexafiuorophosphate prepared from 2 mmol of the cluster-ester and in which this mixture was treated with 6 mmol of triethylsilane gave only CH3CCo3(CO)9 (25%) and HCCo3(CO)9 (45 %) and none of the aldehyde.Reaction of (OC)gCo3CC02CH2C==CCH202CCCo3(CO)g with Dicobalt Octacarbonyl. A 100-ml three-necked flask equipped with a magnetic stirring unit, a nitrogen inlet tube, and a no-air stopper was charged with a solution of the cluster-substituted acetylene (0.42 g, 0.47 mmol) in 20 ml of anhydrous diethyl ether. Subsequently, a solution of 2.3 g (6.7 mmol) of dicobalt octacarbonyl in 50 ml of diethyl ether was added. The mixture was stirred under nitrogen at room temperature for 90 min, during which time a very slow gas evolution and the separation of a solid were observed. The so...

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Section: Methodsmentioning

confidence: 99%

Intramolecular metal-double bond interactions. VI. Metal-.pi.-electron interactions observed in trialkenylaluminum and -gallium derivatives

Dolzine¹,

Oliver²

1974

J. Am. Chem. Soc.

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“…Synthesis of Diuinylmercury Compounds.-The previously unreported divinylmercury compounds (7), ( 9), (lo), (25), and (26) were produced by a standard procedure from the corresponding vinyl bromide. The bromide was converted uia the Grignard reagent to the vinylmercury bromide, which was treated with tin(Ir) chloride or potassium iodide to give the divinylmercury compound.…”

Section: Phmentioning

confidence: 99%