| 154033-84-8

• CAS: 154033-84-8
• 化学式: C₁₂H₂₂B₉FMoO₅
• 分子量: 458.541
• InChiKey: OHRYGMNBCNDGOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  四氟硼酸-二乙醚络合物 、 在 carbon monoxide 作用下， 以 二氯甲烷 为溶剂， 以44%的产率得到
  参考文献：
  名称：

  Allyl carborane complexes of molybdenum and tungsten: cage-hydride abstraction reactions in the presence of donor molecules

  摘要：

  Treatment of the sets [NEt4] [Mo(CO)2(eta3-C3H5)(eta5-7,8,-R'2-7,8-C2B9H9)]dagger (R' = H (1a) or Me (1b)) in CH2Cl2 With [CPh3][BF4] in the presence of donor molecules L affords the complexes [Mo(CO)2(eta3-C3H5)(eta5-7,8-R'2-7,8-C2B9H8-10-L)] (R' = H, L = OEt2 (2a); R' = Me, L = OEt2 (2b), thf (tetrahydrofuran) (2d), SMe2 (2e), PPh3 (2f), NCsH5 (2g), or 4,4'-NC5H4C5H4N (2h)). The tungsten compound [W(CO)2(eta3-C3H5)(eta5-7,8-Me2-7,8-C2B9H8-10-OEt2)] (2c) has been similarly prepared from [NEt4][W(CO)2(eta3-C3H5)(175-7,8-Me2-7,8-C2B9H9)] (1c). The structure of 2b has been established by X-ray crystallography. Crystals are triclinic, space group P1BAR (No. 2) with a = 7.106(1) angstrom, b = 9.088(2) angstrom, c = 16.271(2) angstrom, a = 75.08(1)-degrees, beta = 92.77(1)-degrees, gamma = 102.19(1)-degrees, and Z = 2. The molybdenum atom is ligated on one side by two essentially linearly bound CO molecules and the allyl group, the latter adopting an eta3-bonding mode (Mo-C = 2.342(4), 2.234(4), and 2.365(4) angstrom). On the other side, the molybdenum atom is coordinated by the open pentagonal face of the nido-7,8-C2B9 fragment. The boron atom in this face which is in the beta-site with respect to the two carbons carries an OEt2 molecule as an exopolyhedral substituent (B-0 = 1.544(3) angstrom). Thus, 2b is a zwitterionic complex with formally a plus charge on the oxygen atom and a negative charge on the molybdenum atom. Treatment of CH2Cl2 solutions of 2b and 2c, respectively, with K[BH{CH(Me)(Et)}3], followed by addition of [NEt4]-Cl, affords the species [NEt4] [M(CO)2(eta3-C3H5)(eta5-7,8-Me2-7,8-C2B9H8-10-OEt)] (M = Mo (3a) and W (3b)). Similarly, treatment of tetrahydrofuran solutions of 2b-2d with [NEt4]F gives the salts 3a, 3b, and [NEt4] [Mo(CO)2(eta3-C3Hr5){eta5-7,8-Me2-7,8-C2B9H8-10-0(CH2)3CH2F}] (3c), respectively. Protonation (HBF4.Et2O) of the species 3, in CO-saturated CH2CI2 solutions, yields the complexes [M(CO)4(eta5-7,8-Me2-7,8-C2B9H8-10-OEt)] (M = Mo (4a), W (4c)) and [Mo(CO)4{eta5-7,8-Me2-7,8-C2B9H8-10-0(CH2)3CH2F}] (4d), respectively. In CH2Cl2 solutions at room temperature, compound 4a slowly converts to its polytopal isomer [Mo(CO)4(eta5-2,8-Me2-2,8-C2B9H8-10-OEt)](4b). Complexes 4a and 4b react with [W(=CC6H4Me-4)(CO)2(eta5-C5H5)] in CH2CI2 to give, respectively, the isomeric dimetal compounds [MoW(mu-CC6H4Me-4)(CO)3-(eta5-C5H5)(eta5-n,8-Me2-n,8-C2B9H8-10-OEt)] (n = 7, 6a; n = 2, 6b). The structure of 6b has been established by X-ray crystallography. Crystals are monoclinic, space group C2/c (No. 15) with a = 28.763(3) angstrom, b = 10.950(3) angstrom, c = 18.030(1) angstrom, beta = 94.785(7)-degrees, and Z = 8. The Mo-W bond (2.645(1) angstrom) is spanned by the p-tolylmethylidyne group (mu-C-Mo = 2.088(7) angstrom, mu-C-W = 1.961(7) angstrom). The tungsten atom as expected carries the C5H5 ring and a CO molecule, while the molybdenum atom is coordinated by two CO groups and is also bonded to the five atoms in the open CBBBB face of the carborane cage, forming with the latter an icosahedral 2,1,8-MoC2B9 framework. A boron atom beta to the carbon in the CBBBB ring ligating the molybdenum carries the OEt substituent (B-0 = 1.41 (1) angstrom), and the BH vertex between the BOEt and CMe vertices forms an exopolyhedral B-H half arrow pointing right W linkage (B-W = 2.415(9) angstrom, mu-H-B = 1.11 angstrom, mu-H-W = 1.87 A). The new complexes have been characterized by IR and NMR spectroscopy, in addition to the X-ray diffraction studies.

  DOI：

  10.1021/om00013a026