cis,trans-Os(hydrido)2(NO)(P(iPr)3)2(Cl) | 132621-19-3

• 英文名称: cis,trans-Os(hydrido)2(NO)(P(iPr)3)2(Cl)
• 英文别名: cis,trans-Os(H)2Cl(NO)(P(iPr)3)2
• CAS: 132621-19-3
• 化学式: C₁₈H₄₄ClNOOsP₂
• 分子量: 578.154
• InChiKey: CTGDHWURGJTDKL-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  cis,trans-Os(hydrido)2(NO)(P(iPr)3)2(Cl) 、 silver tetrafluoroborate 以 甲苯 为溶剂， 以83%的产率得到
  参考文献：
  名称：

  Yandulov, Dmitry V.; Streib, William E.; Caulton, Kenneth G., Inorganica Chimica Acta, 1998, vol. 280, # 1-2, p. 125 - 137

  摘要：

  DOI：
• 作为产物：
  描述：

  trans-[OsCl(NO)(P-i-Pr3)2] 在 H₂ 作用下， 以 甲苯 为溶剂， 以92%的产率得到cis,trans-Os(hydrido)2(NO)(P(iPr)3)2(Cl)
  参考文献：
  名称：

  Werner, Helmut; Michenfelder, Annette; Schulz, Michael, Angewandte Chemie, 1991, vol. 103, p. 617 - 618

  摘要：

  DOI：

文献信息

• Conventional Lithium Bases as Unconventional Sources of Methyl Anion:  Facile Me−Si and Me−C Bond Cleavage in RLi, R₂NLi, and BR₄^- by an Electrophilic Osmium Dihydride
  作者：Dmitry V. Yandulov、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/om0200104

  日期：2002.9.1

  and compete for the Os with, the original base, the unsaturated silicon species formed by Si−Me cleavage react with the remaining base by 1,2-addition of (N,C)-Li, forming intermediates that are also reactive by β-Me- transfer. A complex mixture of Os-free coproducts is obtained in both cases. The structural features of 1+ responsible for its unusual reactivity are discussed.

  顺式，反式-OS（H）2（OTf）（NO）（P i Pr 3）2（1-OTf）和OS（H）2（NO）（P i Pr 3）的其他几种前体（1-X））2 +（1 +）与（ME反应3 Si）的2 NLi等，（ME 3 Si）的2 CHLi，锂2,2,6,6-四甲基（TMPLi）中，Me 3 SICH 2 Li和B（CH 2森达3）4 -由一个极不寻常的，轻便β-ME -转移，对于在非极性溶剂的前两个专属的反应途径。已经检验了一系列烷基锂和烷基酰胺和有机硼酸试剂以显示直接β-R的普遍发生“ -转移（R” = H，Me）的给OS电体，是用于完全选择性β-H -在β-我-，唯一（令人惊讶的）NpLi例外。的β-R“消除被排除作为净β-R的机构” -转移为两个代表性的RLi例R” = H，Me和单电子转移机理被证明是不起作用为tetraalkylborates。机理研究还揭示了Li在RLi和R 2 NL
• Structural Distortions in <i>mer</i>-M(H)₃(NO)L₂ (M = Ru, Os) and Their Influence on Intramolecular Fluxionality and Quantum Exchange Coupling
  作者：Dmitry V. Yandulov、Dejian Huang、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/ic991452j

  日期：2000.5.1

  spectra, in addition to chemical exchange. On the basis of experimental and theoretical results, a dihydrogen intermediate is suggested to mediate hydride site exchange in 1. The cis H-M-H distortion shortens the tunneling path for the exchanging hydrides in 1, thereby increasing the tunneling rate; diminishes the "conflict" between trans hydrides in the mer geometry; and decreases the nucleophilicity

  mer-M（H）3（NO）L2类型的分子[M = Ru（1），Os（2）; L = PR3]的特征在于1H NMR T1min值和IR光谱为拟八面体三氢化物，通过将顺式HMH角压缩到大约75度而明显变形。DFT（B3LYP）计算合理化了六坐标d6配合物的畸变，这是由于H-to-sσ捐赠增加以及线性NO +具有出色的pi接受能力所致。在1和2中，氢化物都会经历分子内的位点交换，取决于L，δHHH ++（1）= 10-11 kcal / mol，δHHH ++（2）= 16-20 kcal / mol，而mer-Ru（H） 3（NO）（PtBu2Me）2（1b）除化学交换外，在低温1H NMR光谱中具有适度的交换耦合（高达77 Hz）。根据实验和理论结果，建议使用二氢中间体介导1中的氢化物位交换。顺式HMH变形缩短了1中交换氢化物的隧穿路径，从而提高了隧穿速率。减少了mer几何中反氢化物之间的
• NO binds to unsaturated Os(IV) polyhydrides as a redox reagent
  作者：Joo-Ho Lee、Andrei N. Vedernikov、David Dye、Kenneth G. Caulton

  DOI：10.1016/j.jorganchem.2007.01.059

  日期：2007.7

  Reaction of Os(H)(3)ClL2(L=(PPr3)-Pr-i) with equimolar NO occurs via a detectable paramagnetic species, to form OsCl(NO)L-2 + H-2, then Os(H)(2)Cl(NO)L-2, together with the product of halogen transfer, OsHCl2(NO)L-2. For comparison, equimolar NO and the dichloride Os(H)(2)Cl2L2 react to give OsHCl2(NO)L-2. DFT(PBE) calculations on potential radical intermediates reveal cases where spin density is on NO (vs. on Os), and show how coordinated H-2 can lead to the observed halogen transfer. (c) 2007 Elsevier B.V. All rights reserved.
• Werner, Helmut; Flügel, Ruth; Windmüller, Bettina, Organometallics, 1995, vol. 14, # 2, p. 612 - 618
  作者：Werner, Helmut、Flügel, Ruth、Windmüller, Bettina、Michenfelder, Annette、Wolf, Justin

  DOI：——

  日期：——
• Os(H)₂NO(PⁱPr₃)₂⁺:  Mechanism and Energetics of a Room Temperature Reversible Ethyl/Hydridoethylene Equilibrium and Contrasting Double Insertion of Acetylene
  作者：Dmitry V. Yandulov、John C. Bollinger、William E. Streib、Kenneth G. Caulton

  DOI：10.1021/om000901g

  日期：2001.5.1

  cis,trans-Os(H)(2)(NO)L-2(+) (L = (PPr3)-Pr-i) rapidly adds ethylene to give an eta (2)-ethylene complex with C2H4 trans to one hydride and cis to the other. One hydride and the four ethylene protons are exchanging reversibly above -20 degreesC, with a measured DeltaG(double dagger) (20 degreesC) of 15 kcal/mol. DFT calculations on the rearrangement reveal bond making and breaking, as well as migration of the nonexchanging hydride. Nitrosyl bending is not involved. Use of acetylene leads to insertion into both Os-H bonds; the resulting Os(CH=CH2)(2)(NO)L-2(+) was fully characterized as having inequivalent vinyl groups and undergoes facile vinyl ligand site exchange in solution.