SYNTHESIS, STRUCTURE AND HYDROGENATION OF ETA-3-BENZYL DIPHOSPHINE COMPLEXES OF RHODIUM AND IRIDIUM
SYNTHESIS, STRUCTURE AND HYDROGENATION OF ETA-3-BENZYL DIPHOSPHINE COMPLEXES OF RHODIUM AND IRIDIUM
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DOI：
10.1016/0022-328x(93)80212-t
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发表时间：
1993-02-23
影响因子：
2.3
通讯作者：
RETTIG, SJ
中科院分区：
文献类型：
--
作者：
FRYZUK, MD;MCCONVILLE, DH;RETTIG, SJ
描述了从[(COD)Rh]2(mu-Cl)2开始，通过添加Zn(CH2Ph)或Mg(CH2Ph)2(THF)2来制备(COD)Rh(eta3-CH2Ph)。将大螯合二膦 tBu2P(CH2)3PtBu2、iPr2P(CH2)3PiPr2、iPr2P(CH2)2PiPr2、iPr2PCH2PiPr2 和 Cy2PCH2PCy2 添加到 (COD)Rh(eta3-CH2Ph) 中，产生以下形式的配位不饱和四配位铑配合物P2Rh(eta3-CH2Ph)。 P2Ir(eta3-CH2Ph) 形式的铱配合物（其中 P2 = tBu2P(CH2)3PtBu 和 iPr2P(CH2)3PiPr2）可以由 [P2Ir]2(mu-Cl) 和 Zn(CH2Ph)2 或 Mg(CHPh)2(THF)2 制备。苄基配合物与 H-2 (1 atM) 的反应产生不同组成的双核氢化物衍生物，具体取决于配位二膦的螯合环大小。对于主链中仅具有单个亚甲基的二膦，形成双核六氢化物络合物，其中二膦是双核的。 {iPr2P(CH22)3PiPr2}Rh(eta3-CH2Ph) 的 X 射线结构显示出关于铑的正方形平面几何形状，在 eta3 配位的苄基片段中具有交替的单键和双键。 (1,3-双(二异丙基膦)丙烷}铑(eta3-苄基)晶体为单斜晶系，a = 10.540(3)，b = 15.030(9)，c = 14.858(5)埃，β = 92.91(3)-度，Z = 4，D(c) = 1.329 g cm-3，该结构通过 Patterson 方法求解，并通过全矩阵最小二乘法细化至 R = 0.036 和 R(w) = 0.043，其中 I > 3sigma(I)。
The preparation of(COD)Rh(eta3-CH2Ph) is described starting from [(COD)Rh]2(mu-Cl)2 by the addition of either Zn(CH2Ph), or Mg(CH2Ph)2(THF)2. The addition of the bulky chelating diphosphines tBu2P(CH2)3PtBu2, iPr2P(CH2)3PiPr2, iPr2P(CH2)2PiPr2, iPr2PCH2PiPr2 and Cy2PCH2PCy2 to (COD)Rh(eta3-CH2Ph) yields the coordinatively unsaturated, four-coordinate rhodium complexes of the form P2Rh(eta3-CH2Ph). Iridium complexes of the form P2Ir(eta3-CH2Ph)(where P2 = tBu2P(CH2)3PtBu, and iPr2P(CH2)3PiPr2) can be prepared from [P2Ir]2(mu-Cl), and Zn(CH2Ph)2 or Mg(CHPh)2(THF)2. Reaction of the benzyl complexes with H-2 (1 atM) yields binuclear hydride derivatives of varying composition depending on the chelate ring size of the coordinated diphosphine. For the diphosphines with only a single methylene in the backbone, binuclear hexahydride complexes are formed in which the diphosphine is binucleating. The X-ray structure of {iPr2P(CH22)3PiPr2}Rh(eta3-CH2Ph) shows a square planar geometry about rhodium with alternating single and double bonds in the eta3-coordinated benzyl fragment. Crystals of (1,3-bis(diiso-propylphosphino)propane}rhodium(eta3-benzyl) are monoclinic, a = 10.540(3), b = 15.030(9), c = 14.858(5) angstrom, beta = 92.91(3)-degrees, Z = 4, D(c) = 1.329 g cm-3, space. group P2(1)/n. The structure was solved bv the Patterson method and was refined by full-matrix least-squares procedures to R = 0.036 and R(w) = 0.043 for 4152 reflections with I > 3sigma(I).