The synthesis, properties, and crystal structure of nBu4N[Rh(CO)2(OAc)2], and the exchange of acetate, chloride, and iodide in nBu4N[Rh(CO)2(X)2]
作者:Anthony Fulford、Neil A. Bailey、Harry Adams、Peter M. Maitlis
DOI:10.1016/0022-328x(91)80168-j
日期:1991.10
Evidence was obtained for the formation of a labile mixed anion [Rh(CO)2I(OAC)]− on reaction of [Rh2(CO)4I2] with nBu4N+ OAc−. It is unlikely that the promotional effect of acetate in methyl acetate carbonylation is due to the participation of acetato-rhodium complexes. Since the lithium acetate reacts readily with iodomethane to give lithiumiodide, the observed promotion probably arises from the formation
的反应Ñ卜4 N [RH)CO)2氯2 ],1,用CO下醋酸银,得到二乙酸盐Ñ卜4 N [铑(CO)2(OAc)2,2。该配合物已在光谱上表征[ν(CO term)1986,2066; ν(CO 2-单齿)1615cm -1 ],通过单晶X射线测定。阴离子是平面的,具有单齿乙酸盐,Rh-O 2.074(6)和2.053(7)。配合物2立即与MeI反应生成MeOAc和[Rh(CO)2 I 2 ] -,3,然后通常氧化添加更多的MeI。它还与HCl反应生成HOAC和[Rh(CO)2 Cl 2 ] -。[Rh 2(CO)4 I 2 ]与n Bu 4 N + OAc-反应生成不稳定的混合阴离子[Rh(CO)2 I(OAC)] -的证据。。乙酸盐在乙酸甲酯羰基化中的促进作用不太可能归因于乙酰铑络合物的参与。由于乙酸锂容易与碘甲烷反应生成碘化锂,因此观察到的促进作用可能来自LiI的形成。MeI与n Bu
Kinetic studies of some substituted hexarhodium carbonyl clusters
作者:Claudia Babij、David H. Farrar、Igor O. Koshevoy、Anthony J. Poë、Sergey P. Tunik
DOI:10.1039/b408687b
日期:——
Reactions of the halides X- (X- = chloride, bromide or iodide) with the substituted cluster Rh6(CO)15(PPh3) in oxygen-free chloroform lead to [Rh5(CO)14(PPh3)]-, Rh(CO)2(PPh3)2X and [Rh(CO)2X2]- in the molar ratios 2:1: approximately 13. Oxidation by the solvent is assumed to lead to most of the Rh(I) product, and the stoichiometry for reactions with I- can be defined as 4Rh6(CO)15(PPh3) + 27I- + 12CHCl3
Ionic attachment as a feasible approach to heterogenizing anionic solution catalysts. Carbonylation of methanol
作者:Russell S. Drago、Eric D. Nyberg、Anton El A'mma、Alan Zombeck
DOI:10.1021/ic50217a001
日期:1981.3
Rhodium catalysed methanol carbonylation in the presence of bis(ditertiarybutylphosphinomethyl)benzene
作者:Cristina Jimenez-Rodriguez、Peter J. Pogorzelec、Graham R. Eastham、Alexandra M. Z. Slawin、David J. Cole-Hamilton
DOI:10.1039/b701582h
日期:——
Catalysts prepared in situ from 1,2-(But2PCH2)2C6H4 (DTBPMB) and [RhCl(CO)2]2 catalyse the carbonylation of methanol in the presence of MeI at rates (4.12 and 8.90 × 10−4 mol dm−3 s−1 at 150 and 180 °C respectively) faster than those in the absence of added phosphine, although they decompose to [RhI2(CO)2]− over time. HPIR studies suggest that MeI adds to [Rh(DTBPMB)X(CO)] (X = Cl or I), which have
催化剂类由1,2-(Bu t 2 PCH 2)2 C 6 H 4(DTBPMB)和[RhCl(CO)2 ] 2原位制备可催化羰基化甲醇在MeI的存在下(尽管它们分解为[RhI 2(CO))的速率(分别在150和180°C下分别为4.12和8.90×10 -4 mol dm -3 s -1在150和180°C时)比没有添加膦的情况下更快2 ] -随着时间的流逝。HPIR研究表明,MeI添加到[Rh(DTBPMB)X(CO)](X = Cl或I)中,已分离并充分表征,得到[Rh(DTBPMB)MeI 2(CO)]。[Rh(DTBPMB)MeI 2(CO)]与CO反应生成[Rh(DTBPMB)(C(O)Me)I 2(CO)],但是甲醇 提升 分解[RhI 2(CO)2 ] -和[1,2-(MeBu t 2 PCH 2)2 C 6 H 4)] [I 3 ] 2的分离和表征。HPNMR研究表明,[R