[(hydridotris(pyrazolyl)borato)RuCl2(NO)] | 137729-45-4

• 英文名称: [(hydridotris(pyrazolyl)borato)RuCl2(NO)]
• 英文别名: [(hydridotris(pyrazolyl)borato)RuCl₂(NO)]；[TpRuCl₂(NO)]；RuCl2(hydrotris(pyrazolyl)borate)(nitrosyl)；(hydrotris(pyrazolyl)borate)RuCl2(NO)；[(trispyrazolylborate)RuCl2(NO)]；[(HB(pyrazol-1-yl)3)RuCl2(NO)]；TpRuCl2(NO)
• CAS: 137729-45-4
• 化学式: C₉H₁₀BCl₂N₇ORu
• 分子量: 415.012
• InChiKey: YLQBMZXNVUMZPK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(hydridotris(pyrazolyl)borato)RuCl2(NO)] 在 N(CH₂CH₃)3 、 HBF₄*(CH₃CH₂)2O 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Hydration of Nitrosylruthenium Acetylide Complexes Having a Tris(pyrazol-1-yl)borate in the Presence of Protic Acid:  Formation of Ketonyl and Acyl Complexes

  摘要：

  Treatment of the monoacetylide complexes TpRuCl(CdropCR)(NO) (R = Ph (1a), p-CH3C6H4 (1b), Bu-t (1c), CH2CH2OH (Id), CH2OH (1e), C(Me)(2)OH (1f), C(Ph)(2)OH (1g); Tp = BH(pyrazol-1-yl)(3)) with HBF4.Et2O in methanol afforded the ketonyl complexes TpRuCl-(CH2C(O)R)(NO) (R = Ph (2a), p-CH3C6H4 (2b), Bu-t (2c), CH2CH2OMe (2d), CH2OH (2e)) and the alpha,beta-unsaturated acyl complexes TpRuCl(C(O)CH=CR'(2))(NO) (R' = Me (3f), Ph (3g)), respectively. While the latter were produced by hydration via allenylidene species, the former were presumably generated from the reaction of eta(2)-coordinated 1-alkyne species with adventitious water.

  DOI：

  10.1021/om0303597

文献信息

• NO Migratory Insertion into Ruthenium–Aryl Bond with a Hydridotris(pyrazolyl)borato Ligand
  作者：Yasuhiro Arikawa、Motoki Yamada、Nobuko Takemoto、Shinnosuke Horiuchi、Eri Sakuda、Keisuke Umakoshi

  DOI：10.1021/acs.organomet.0c00694

  日期：2021.2.8

  NO migratory insertion into the [Ru]–Ph bond was clearly revealed. Monophenyl complex [TpRuCl(Ph)(NO)] (2) (Tp = hydridotris(pyrazolyl)borato) was prepared from the reaction of [TpRuCl2(NO)] (1) with diphenylzinc along with the formation of [TpRu(Ph)2(NO)] (3) as a side product. Insertion reaction of 2 with DMAP (4-dimethylaminopyridine) gave rise to a nitrosobenzene complex [TpRuCl(dmap)N(═O)Ph}]

  没有清楚地表明迁移到[Ru] –Ph键中。单苯配合物[TpRuCl（Ph）（NO）]（2）（Tp =氢化三（吡唑基）硼酸酯）是由[TpRuCl 2（NO）]（1）与二苯基锌反应并形成[TpRu（Ph）制备的）2（NO）]（3）作为副产品。2与DMAP（4-二甲基氨基吡啶）的插入反应生成亚硝基苯络合物[TpRuCl（DMAP）N（= O）Ph}]（4）。该过程的动力学通过1 H NMR谱进行了研究。在拟一级条件下，反应速率与DMAP的浓度无关。其激活参数为ΔH⧧ = 18±2千卡摩尔-1，Δ小号⧧ = -36±4卡ķ -1摩尔-1，以及相关的吉布斯活化能Δ ģ ⧧（298K）= 29±2千卡摩尔-1。激活的熵意味着在过渡态中同时包含了复合物2和DMAP。
• Ortho−Nitrosation of Anilines on a Ruthenium Hydridotris(pyrazolyl)borato Complex and Oxidation of the Resulting Coordinated Amine Groups
  作者：Yasuhiro Arikawa、Soseki Yamaguchi、Yuji Otsubo、Masayoshi Onishi、Keisuke Umakoshi

  DOI：10.1021/om5012769

  日期：2015.3.23

  in the case of secondary amines (N-methylanilines 4-NH(Me)C6H4R (R = tBu, H)), similar reactions gave amine-chelated nitroso complexes [TpRuClN(═O)–C6H3R–NHMe-κ2N,N}] (R = tBu (4a), H (4b)) and imine-chelated nitroso complexes [TpRuClN(═O)–C6H3R–N═CH2-κ2N,N}] (R = tBu (5a), H (5b)). Conversion of 4b into 5b by O2 was disclosed by 1H NMR monitoring. Moreover, oxidative reaction of 2a afforded an

  发现邻位苯胺的亚硝化反应是在氢化钌三（吡唑基）硼酸盐（Tp）络合物上进行的。[TpRuCl 2（NO）]（1）与伯苯胺4-NH 2 C 6 H 4 R（R = t Bu，H）在过量Et 3 N存在下于CH 2 Cl 2中的反应得到胺螯合的亚硝基芳烃配合物[TpRuCl N（= O）-C 6 H ^ 3 R-NH 2 -κ 2 ñ，ñ }]（R =吨BU（图2a），H（2b中））。使用2,4,6-三甲基苯胺得到芳基二氮杂烯基络合物[TpRuCl 2 NNC 6 H 2（Me）3 }]（3），因为在邻位引入了Me取代基而不形成亚硝化产物。另一方面，在仲胺（N-甲基苯胺4-NH（Me）C 6 H 4 R（R = t Bu，H））的情况下，相似的反应得到胺螯合的亚硝基配合物[TpRuCl N（═ O）–C 6 H 3 R–NHMe-κ 2 N，N }]（R = t Bu（4a），H（4b））和亚胺-螯合亚硝基络合物[TpRuCl
• NO Insertion Reaction of Ethyl(nitrosyl)ruthenium Complex Having Hydrotris(pyrazolyl)borate and Conversion to Acetaldoxime and Acetonitrile Complexes
  作者：Yasuhiro Arikawa、Shin-ya Tashita、Soseki Yamaguchi、Hitomi Miyahara、Taiki Asayama、Keisuke Umakoshi、Masayoshi Onishi

  DOI：10.1246/cl.2010.940

  日期：2010.9.5

  Ethyl(nitrosyl)ruthenium [TpRuCl(Et)(NO)] (2) was isolated from the reaction of [TpRuCl2(NO)] (1) with LiBHEt3. NO insertion of 2 was observed from heating a solution of 2. In the presence of PPh3,...

  从 [TpRuCl2(NO)] (1) 与 LiBHEt3 的反应中分离出乙基（亚硝基）钌 [TpRuCl(Et)(NO)] (2)。加热 2 的溶液没有观察到 2 的插入。在 PPh3 存在下，...
• N−C Bond Formation of NO Ligands on Ruthenium Complexes with Concurrent Vinylic C−H Activation and Subsequent Proton-Induced Reactivities of the Resulting Nitrosovinyl Species
  作者：Yasuhiro Arikawa、Taiki Asayama、Kazuki Itatani、Masayoshi Onishi

  DOI：10.1021/ja804095u

  日期：2008.8.13

  The N-C coupling of ligating NO with 2-vinylpyridines, affording nitrosovinyl complexes, was found. This is of significance since the reaction process involves a C-H activation of the vinyl moiety and subsequent C-N bond formation. Furthermore, we show that the resulting nitrosovinyl complexes are chemically versatile and potentially valuable species. Protonation of the resulting nitrosovinyl complexes in refluxing alcohol afforded the alcohol-incorporated complexes, as well as the ketoimine species. It is interesting to note that a proton-induced reaction with PPh3 trapped their intermediates, leading to the explication of these reaction mechanisms.
• Triphenylphosphine Incorporation Reactions of Diynyl Complexes Containing a TpRu(NO) Fragment and Isomerization to Ruthenacyclobuta[<i>b</i>]naphthalene
  作者：Yasuhiro Arikawa、Taiki Asayama、Chie Tanaka、Shin-ya Tashita、Misako Tsuji、Kenta Ikeda、Keisuke Umakoshi、Masayoshi Onishi

  DOI：10.1021/om701028r

  日期：2008.3.24

  Nitrosylruthenium arylbutadiynyl complexes having a Tp ligand (Tp = BH(pyrazol-l-yl)(3)) were prepared, and their reactivities toward PPh3 incorporation in the presence of HBF4 center dot Et2O were described. The PPh3 incorporation of mono(arylbutadiynyl) complex TpRuCl(C=C-C=C-C6H4Me)(NO) (1) resulted in the beta-phosphonioalkenyl complex (E)-[TpRuC](CH=C(PPh3)-C=C-C6H4Me)(NO)]BF4 (2 center dot BF4), whereas when bis(arylbutadiynyl) TpRu(C=C-C=C-C6H4Me)(2)(NO) (3) was treated, monoand bis(beta-phosphonioalkenyl) complexes (E)-[TpRu(C=C-C=C-C6H4Me)(CH=C(PPh3)-C=C- C6H4Me)(NO)]BF4(4 center dot BF4) and (E, E)-[TpRu(CH=C(PPh3)-C=C-C6H4Me)(2)(NO)](BF4)(2) 5 center dot(BF4)(2)} were obtained depending oil the reaction conditions. On the other hand, an unsymmetrically mixed (arylbutadiynyt)(3-hydroxyalkynyl) complex, TpRu(C=C=C=C6H4Me) C=CCPh2(OH)} (NO) (6), was allowed to react with PPh3 in the presence of the protic acid to give the alpha-phosphonioallenyl [TpRu(C=C-C=C-C6H4Me)C(PPh3)=C=CPh2}(NO)]BF4 (7 center dot BF4). Interestingly, thermal isomerization of 7 center dot BF4 to a ruthena-2-PPh3-cyclobutal[b]naphthalene [TpRuf CH(PPh3)[3-Ph-8-(MeC6H4-C=C)-C10H4]}(NO)]BF4 (8 center dot BF4) was observed.