DEUTERIUM CYANIDE

DCN DEUTERIUM CYANIDE 798.8279 -1.7354E+04 -3.4780E+02 4.9610E-01 -2.8192E... 

Reactions of the HNiL3CN complex with 1,3-cyclopentadiene, 1,3-cyclo-hexadiene, and 1,3-cyclooctadiene gave intermediates with decreasing stabilities in that order the 1,3-cyclooctadiene intermediate was not spectroscopically observable. The cyclohexadiene adduct was shown to be the cyclohexadienyl complex 12 by its proton spectra, with resonances of H , Hb, and —(CH2)3— at 14.53, 6.06, and 8.47, respectively these values are close to the chemical shifts found earlier (51) for 13 14.52,5.86, and 8.48. The reaction of DNi[P(OMe)3]X with cyclopentadiene gives 13-d, with addition of D and Ni to the same side of the ring (52). Backvall and Andell (55) have shown, using Ni[P(OPh)3]4 and deuterium cyanide (DCN), that addition of D and CN to cyclohexadiene is stereospecifically cis, as expected for jt-allyl intermediate 12. 

The stereoselectivity of the reaction was the target of several investigations. The results clearly establish that the addition of hydrogen cyanide to olefins is stereospecifically syn [33, 46 9]. Thus, reaction of terminal, deuterium-substituted olefins yields the corresponding syn addition products. Hydrocyanation of 4-t-butyl cyclohex-1-ene with deuterium cyanide confirmed these results. It is found that the stereospecifity is independent of the catalyst metal employed, since both nickel° and palladium catalysis give the syn addition products [50]. 

Nagate, T., Kondow, T., Ozaki, Y., and Kuchitsu, K. 1981. Absorption spectra of hydrogen cyanide and deuterium cyanide in the 130-80 nm range. Chemical Physics, 57 45-53. 

DCN DEUTERIUM CYANIDE 25.967 3.7969E-02 -1.2416E-05 -3.2240E-09 2.2610E-12 100 1500 gas... 

Similar results arc obtained with addition of hydrogen cyanide or deuterium cyanide to dcutcr-ated and nondeuterated alkenes, norbornene and anchored cyclohexenes in the presence of Pd(Diop)2 as the catalyst precursor20-24. Steric requirements in the substrate are crucial. Thus, 7,7-dimethylnorbornene is not hydrocyanated and 4-/m-butylcyclohexene only gives the equatorial product (vide infra)10-24. 

The reaction of ( )-3,3-dimethyl-l-butene-l,2-r/2 with hydrogen cyanide and of ( )-3,3-dimethyl-l-butene-l-d2 with deuterium cyanide stereospecifically proceeds in a cis fashion with Pd(Diop)2 used as the catalyst precursor20,24. The stereochemistry of the products is verified by NMR and characterization of the thiourea derivatives of the corresponding amine obtained with lithium aluminum deuteride. No //wu-addition products exceeding a limit of 5-10% can be detected. 

Employing the same palladium catalysts as above selective cisjexo addition of deuterium cyanide to norbornene and norbornadiene was achieved20,24. 

VIII. FAR INFRARED SPECTRUM OF POLYCRYSTALLINE HYDROGEN AND DEUTERIUM CYANIDE. 

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