(C6H5)3PNP(C6H5)3*{Ru3(μ3-η2-S(C5H4N))(CO)9} | 130352-22-6

• 英文名称: (C6H5)3PNP(C6H5)3*{Ru3(μ3-η2-S(C5H4N))(CO)9}
• 英文别名: [PPN][Ru3(μ3-η(2)-SNpy)(CO)9]
• CAS: 130352-22-6
• 化学式: C₁₄H₄NO₉Ru₃S*C₃₆H₃₀NP₂
• 分子量: 1204.05
• InChiKey: XCEKJHPGIUAZGZ-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

• 作为反应物：
  描述：

  (C6H5)3PNP(C6H5)3*{Ru3(μ3-η2-S(C5H4N))(CO)9} 、 三丁基膦 以 四氢呋喃 为溶剂， 以80%的产率得到[PPN][Ru3(μ3-η(2)-Spy)(CO)7(P(n-Bu)3)2]
  参考文献：
  名称：

  Kinetic Studies on Reactions of Activated Triruthenium Carbonyl Clusters with Phosphorus Ligands

  摘要：

  Reactions of the cluster complexes [PPN][Ru-3(mu(3)-eta(2)-Xpy)(CO)(9)] (1-3) (Xpy = 2-substituted pyridyl group; 1, X = PhN; 2, X = MeN; 3, X = S) with phosphines in THF solution are described. Complex 1, containing the 2-anilinopyridyl group, reacts with P(n-Bu)(3) or PPh(3) at room temperature to yield the addition product [PPN]-(Ru-3(mu-eta(2)-PhNpy)(CO)(9)L] (4a,b) (a, L = P(n-Bu)(3); b, L = PPh(3)). This adduct slowly loses either the phosphine or a CO ligand to give a mixture of the starting antecedent species and its monosubstituted derivative. The corresponding intermediate adducts are not seen with 2-(methylamino)pyridyl and 2-thiopyridyl complexes 2 and 3 which react with P(n-Bu)(3) to yield respectively the monosubstituted complex [PPN][Ru-3(mu(3)-eta(2)-MeNpy)(CO)(8)P-(n-Bu)(3)] (5a) and the disubstituted complex [PPN][Ru-3(mu(3)-eta(2)-Spy)(CO)(7)(P(n-Bu)(3))(2)] (6a). Kinetic results for these reactions are reported. The reactions are first-order in complex and first-order in ligand concentrations. It is proposed that the initial step for these reactions is an associative nucleophilic attack of phosphine ligands on the metal atom accompanied by opening of the mu-X bridge bond to form the adducts [PPN][Ru-3(mu-eta(2)-Xpy)-(CO)(9)L]. The rates of reaction increase in the order 2-MeNpy < 2-Spy < 2-PhNpy. The reactivity order of these complexes toward nucleophiles is discussed in terms of electronic effects of their ancillary ligands.

  DOI：

  10.1021/ic950947f
• 作为产物：
  描述：

  K{Ru3(μ3-η2-S(C5H4N))(CO)9} 、 双(三苯基正膦基)氯化铵 以 甲醇 为溶剂， 以80-90的产率得到(C6H5)3PNP(C6H5)3*{Ru3(μ3-η2-S(C5H4N))(CO)9}
  参考文献：
  名称：

  Activation of triruthenium carbonyl complexes by incorporation of hemilabile ancillary ligands containing alkoxo, amido, or thiolato groups. Generation of a reactive alkenyl complex

  摘要：

  The alkoxo, amido, or thiolato groups derived respectively from 2-hydroxypyridine, 2-anilinopyridine, or 2-mercaptopyridine are incorporated into Ru3(CO)12 to give several ''activated'' anionic and neutral complexes. The anions [Ru3(mu-eta(2)-X(C5H4N))(CO)10]- (1a,c) and [Ru3(mu(3)-eta(2)-X(C5H4N))(CO)9]- (2a,b): a, X = N(C6H5); b, X = S; c, X = O) are obtained (i) in 80-90% yield by treatment of Ru3(CO)12 with K[X(C5H4N)] followed by metathesis with (PPN)Cl (PPN = (C6H5)3PNP(C6H5)3+) or (ii) by reaction of HX(C5H4N) with PPN[Ru3(mu-H)(CO)11] (refluxing THF, 2 h, 60% yield). The amido derivatives 1a-3a are also available via method iii, involving direct reaction of 2-anilinopyridine with Ru3(CO)12 (refluxing benzene, 2 h) to give Ru3(mu-H)(mu-(3)-eta(2)-N(C6H5)(C5H4N))(CO)9 (3a) (yield 85%). The latter is subsequently deprotonated by PPNBH4 to give 2a (yield 90%). The sulfido derivative Ru3(mu-H)(mu(3)-eta(2)-S(C5H4N))(CO)9 (3b) is obtained in 80-90% yield by protonation of the potassium salt of 2b. The X-ray structures of the PPN salts of 1c and 2a are reported. Crystallographic data for PPN.1c: triclinic P1BAR (No. 2), a = 13.209 (1) angstrom, b = 18.149 (2) angstrom, c = 11.217 (2) angstrom, alpha = 102.37 (1)-degrees, beta = 96.52 (1)-degrees, gamma = 107.40 (1)-degrees, V = 2461 angstrom 3, Z = 2; mu(Mo K-alpha) = 10.15 cm-1; R = 0.042, R(w) = 0.043 for 7330 observations and 382 variables. Crystallographic data for PPN.2a: triclinic P1BAR (No. 2), a = 15.933 (2) angstrom, b = 17.163 (2) angstrom, c = 10.384 (2) angstrom, alpha = 102.69 (1)-degrees, beta = 91.06 (1)-degrees, gamma = 107.55 (1)-degrees, V = 2630 angstrom 3, Z = 2; mu(Mo K-alpha) = 8.64 cm-1; R = 0.042, R(w) = 0.042 for 5665 observations and 364 variables. On the basis of these structures, it is suggested that the variable hapticity of group X (terminal position in 1 and bridging position in 2) plays a ''lightly stabilizing'' role for coordination sites. The hydrido complexes Ru3(mu-H)(mu(3)-eta(2)-X(C5H4N))(CO)9 (3a,b) react cleanly with alkynes (40-50-degrees-C, 30-45 min) to give selectively the corresponding alkenyl complexes Ru3(mu(3)-eta(2)-X(C5H4N))(mu-(C6H5)CCH(C6H5))(CO)8 (4a, 90-95% yield; 4b, 70-80% yield) via cis insertion into the metal-hydride bond. The X-ray structure of 4a has been determined. Crystallographic data for 4a (crystallizing with 1 mol of CH2Cl2 per unit cell): triclinic P1BAR (No. 2), a = 10.424 (1) angstrom, b = 18.795 (2) angstrom, c = 8.964 (1) angstrom, alpha = 93.97 (1)-degrees, beta = 105.09 (1)-degrees, gamma = 78.51 (1)-degrees, V = 1661 (5) angstrom 3, Z = 2; mu(Mo K-alpha) = 13.76 cm-1; R = 0.023, R(w) = 0.025 for 5502 reflections and 436 variables. The cluster consists of a trinuclear ruthenium unit supported by a face-bridging phenylpyridylamido group. The bridging alkenyl group is coordinated at equatorial sites and spans a metal-metal edge adjacent to that supported by the bridging amido group. There is a bridging carbonyl spanning the same edge as the amido group. The features which may account for the high reactivity of this complex are discussed.

  DOI：

  10.1021/om00039a046