The reaction of [NiL4](L = PEt3 or PBun3) with CO2 in toluene affords complexes of formula [Ni(CO2)L2], via the [Ni(CO2)L3] species. The reaction of [Ni(CO2)P(C6H11)3}2]·0.75C6H5Me with O2 to give (peroxocarbonato)-bis( tricyclohexylphosphine)nickel(II) is also reported.
[NiL 4 ](L = PEt 3或PBu n 3)与CO 2在甲苯中的反应通过[Ni(CO 2)L 3 ]物种提供式[Ni(CO 2)L 2 ]的配合物。还报道了[Ni(CO 2)P(C 6 H 11)3 } 2 ]·0.75C 6 H 5 Me与O 2的反应,生成(过氧羰基)-双(三环己基膦)镍(II)。
Sibille, Soline; Folest, Jean-Claude; Coulombeix, Jose, Journal of Chemical Research - Part S
作者:Sibille, Soline、Folest, Jean-Claude、Coulombeix, Jose、Troupel, Michel、Fauvarque, Jean-Francois、Perichon, Jacques
DOI:——
日期:——
Synthesis and fluxional behavior of [bis(trialkylphosphine)nickelio]anthracene (alkyl = Et, Bu)
作者:Amnon Stanger、K. Peter C. Vollhardt
DOI:10.1021/om00037a054
日期:1992.1
The title compounds were prepared from the respective (R3P)2NiCl2 complexes and magnesium-anthracene-(THF)3 (or anthracene in the presence of Mg or C8K). The assignment of the anthracene proton NMR signals using NOE in conjunction with magnetization-transfer techniques is described. The complexes undergo haptotropic rearrangements in which the (R3P)2Ni moiety migrates between the two terminal rings of the coordinated anthracene. The rates of these processes are concentration independent and unaffected by the presence of free anthracene and tris(trialkylphosphine)nickel. Kinetic studies in the temperature range -60 to +70-degrees-C using line shape analysis and spin saturation transfer techniques were carried out. It was found that DELTA-H double-ended-dagger = 13.6 kcal mol-1 and DELTA-S double-ended-dagger = -4.3 eu for the haptotropic rearrangement in 2, and similar values were found for 1. Possible mechanisms are discussed. According to H-1, C-13, and P-31 NMR data, the coordination number between the anthracene and the (R3P)2Ni moiety is 4. However, an equilibrium between two eta(2) structures with DELTA-G double-ended-dagger less-than-or-equal-to 4 kcal mol-1 cannot be ruled out.