(nitrato-O)(nitrato-O,O')(η-pentamethylcyclopentadienyl)rhodium(III) | 55971-81-8

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (nitrato-O)(nitrato-O,O')(η-pentamethylcyclopentadienyl)rhodium(III)
• 英文别名: [(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η1-NO3)(η2-NO3)]；[(η-5-cyclopentadienyl)Rh(η1-NO3)(η2-NO3)]；(η5-C5Me5)Rh(η2-NO3)(η1-NO3)；[Cp*Rh(η1-NO3)(η2-NO3)]；1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);dinitrate
• CAS: 55971-81-8；74463-20-0
• 化学式: C₁₀H₁₅N₂O₆Rh
• 分子量: 362.144
• InChiKey: GITDJKJIIVAOQU-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：

  sodium azide 、 (nitrato-O)(nitrato-O,O')(η-pentamethylcyclopentadienyl)rhodium(III) 以 二氯甲烷 为溶剂， 以89.2%的产率得到[(1,2,3,4,5-pentamethylcyclopentadienyl)Rh(η1-NO3)(η1,μ-N3)]2
  参考文献：
  名称：

  NO bond cleavage and various bonding modes of the nitrato ligand in rhodium complexes: syntheses and structures of [Cp*Rh(η1-NO3)(μ-Cl)]2, {[Cp*RhCl(PPh3)(CNC6H11)]2(NO2)(NO3)}·2H2O, [Cp*Rh(η1-NO3)(η1,μ-N3)]2, [Cp*Rh(η2-NO3)(O3SCF3)], trans-{[Rh(PPh3)2(CN2,6-Me2C6H3)2](NO3)}·H2O, and {[Cp*2Rh2(η2,μ-NO2-N,O)2(η1,μ-N3)](PF6)}·0.5H2O

  摘要：

  The addition of 2 equiv. of AgNO3 to a dinuclear chloro-bridged Rh(III) compound, [Cp*RhCl2](2), resulted in the replacement of the terminal chloro ligand to give [Cp*Rh(eta(1)-NO3)(mu-Cl)](2) (1). On the other hand, the reaction of [Cp*RhCl2](2) with 4 equiv. of AgNO3 led to the formation of a mononuclear bis(nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(2)-NO3)] (2). Compound 1 reacted With PPh3 and cyclohexyl isocyanide (CN-C6H11) to give a chiral compound, {[Cp*RhCl(PPh3)(CN-C6H11)](2)(NO2)(NO3)} 2H(2)O (3.2H(2)O), which shows an unusual example of the nitrate-to-nitrite reduction in the rhodium coordination sphere. The reaction of compound 2 with either NaN3 or N3SiMe3 gave a dinuclear (eta(1)-nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(1),mu-N-3)](2) (4). On the other hand, on addition of silver triflate (AgOTf), compound 2 underwent replacement to give a monormclear (eta(2)-nitrato)-rhodium compound, [Cp*Rh(eta(2)-NO3)(OTf)] (5). In addition, compound 2 reacted with a mixture of PPh3 and 2,6-dimethylphenyl isocyanide (CN-2,6-Me2C6H3) to give trans-{[Rh(PPh3)(2)(CN-2,6-Me2C6H3)(2)](NO3)} . H2O (6. H2O), Which exhibits the complete elimination of all ligands in compound 2 and indicates the formal reduction of the rhodium metal from + 3 to + 1. The nitro-rhodium compound, {[Cp-2*Rh-2(eta(2), mu-NO2-N,O)(2)(eta(1),mu-N-3)](PF6)} . 0.5H(2)O (7 . 0.5H(2)O), was prepared by the reaction of [Cp*RhCl(dppf)](PF6) (dppf = Fe(eta(5) -C5H4PPh2)(2)) with a mixture of N3SiMe3 and AgNO3, Which also displays the N-O bond cleavage of nitrate (NO3-) to nitrite (NO2-). The structures of 1, 3 . 2H(2)O, 4, 5, 6 - HO, and 7 . 0.5H(2)O were determined by X-ray diffraction. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01466-4
• 作为产物：
  描述：

  dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 silver nitrate 以 二氯甲烷 、 丙酮 为溶剂， 以93.1%的产率得到(nitrato-O)(nitrato-O,O')(η-pentamethylcyclopentadienyl)rhodium(III)
  参考文献：
  名称：

  NO bond cleavage and various bonding modes of the nitrato ligand in rhodium complexes: syntheses and structures of [Cp*Rh(η1-NO3)(μ-Cl)]2, {[Cp*RhCl(PPh3)(CNC6H11)]2(NO2)(NO3)}·2H2O, [Cp*Rh(η1-NO3)(η1,μ-N3)]2, [Cp*Rh(η2-NO3)(O3SCF3)], trans-{[Rh(PPh3)2(CN2,6-Me2C6H3)2](NO3)}·H2O, and {[Cp*2Rh2(η2,μ-NO2-N,O)2(η1,μ-N3)](PF6)}·0.5H2O

  摘要：

  The addition of 2 equiv. of AgNO3 to a dinuclear chloro-bridged Rh(III) compound, [Cp*RhCl2](2), resulted in the replacement of the terminal chloro ligand to give [Cp*Rh(eta(1)-NO3)(mu-Cl)](2) (1). On the other hand, the reaction of [Cp*RhCl2](2) with 4 equiv. of AgNO3 led to the formation of a mononuclear bis(nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(2)-NO3)] (2). Compound 1 reacted With PPh3 and cyclohexyl isocyanide (CN-C6H11) to give a chiral compound, {[Cp*RhCl(PPh3)(CN-C6H11)](2)(NO2)(NO3)} 2H(2)O (3.2H(2)O), which shows an unusual example of the nitrate-to-nitrite reduction in the rhodium coordination sphere. The reaction of compound 2 with either NaN3 or N3SiMe3 gave a dinuclear (eta(1)-nitrato)-rhodium compound, [Cp*Rh(eta(1)-NO3)(eta(1),mu-N-3)](2) (4). On the other hand, on addition of silver triflate (AgOTf), compound 2 underwent replacement to give a monormclear (eta(2)-nitrato)-rhodium compound, [Cp*Rh(eta(2)-NO3)(OTf)] (5). In addition, compound 2 reacted with a mixture of PPh3 and 2,6-dimethylphenyl isocyanide (CN-2,6-Me2C6H3) to give trans-{[Rh(PPh3)(2)(CN-2,6-Me2C6H3)(2)](NO3)} . H2O (6. H2O), Which exhibits the complete elimination of all ligands in compound 2 and indicates the formal reduction of the rhodium metal from + 3 to + 1. The nitro-rhodium compound, {[Cp-2*Rh-2(eta(2), mu-NO2-N,O)(2)(eta(1),mu-N-3)](PF6)} . 0.5H(2)O (7 . 0.5H(2)O), was prepared by the reaction of [Cp*RhCl(dppf)](PF6) (dppf = Fe(eta(5) -C5H4PPh2)(2)) with a mixture of N3SiMe3 and AgNO3, Which also displays the N-O bond cleavage of nitrate (NO3-) to nitrite (NO2-). The structures of 1, 3 . 2H(2)O, 4, 5, 6 - HO, and 7 . 0.5H(2)O were determined by X-ray diffraction. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01466-4

文献信息

• Systematic Heterodinuclear Complexes with MM′(μ-meppp) Centers That Tune the Properties of a Nesting Hydride (M = Ni, Pd, Pt; M′ = Rh, Ir; H₂meppp = <i>meso</i>-1,3-Bis[(mercaptoethyl)phenylphosphino]propane)
  作者：Bunsho Kure、Mikie Sano、Takayuki Nakajima、Tomoaki Tanase

  DOI：10.1021/om500410f

  日期：2014.8.11

  and PtIIRhIII ([6c]NO3) complexes, the hydrides were extremely unstable and were likely to undergo an unusual metal-to-Cp* ring hydrogen transfer, resulting in η4-C5Me5H MIIRhI complexes, [M(μ-meppp)Rh(η4-C5Me5H)]NO3 (M = Pd ([7b]NO3), Pt ([7c]NO3)). The property of the hydride was drastically switched by varying the anchoring metal ions of the M′ site (Rh, Ir); that of [6a]NO3 (M′ = Rh) is not protic

  具有P 2 S 2配体[M（meppp）]（M = Ni（1a），Pd（1b），Pt（1c）； H 2 meppp =中观-1,3-双[（巯基乙基）苯基膦基]丙烷），用[* M'CP氯处理2 ] 2或[M'CP *（NO 3）2 ]（CP * =η 5 -五甲基），得到一系列bisthiolate桥连中号II M' III异核复合物，[M（μ-meppp）M'CP * X] X'（M = Ni，Pd，Pt; M'= Rh，Ir; X = Cl，NO 3 ; X'= Cl，PF 6，NO 3）。硝酸盐络合物[M（μ-meppp）-M'CP *（NO 3）] NO 3（M'= Rh（[ 4a – c ] NO 3），Ir（[ 5a – c ] NO 3）; M = Ni（a），Pd（b），Pt（c））进一步与甲酸钠在水或甲醇中反应，转化为双硫醇盐和氢化物桥接的配合物[M（μ-meppp）（μ-H）M'
• (η⁵-Pentamethylcyclopentadienyl)rhodium and -iridium Complexes with Weakly and Strongly Coordinating Anions:  Isolation and First X-ray Molecular Structures of the Tris(solvent) Complexes [(C₅Me₅)M(acetone)₂(H₂O)][BF₄]₂ (M = Rh, Ir)
  作者：Hani Amouri、Carine Guyard-Duhayon、Jacqueline Vaissermann、Marie Noelle Rager

  DOI：10.1021/ic010772b

  日期：2002.3.1

  Several novel pentamethylcyclopentadienyl complexes of general formula [(C5Me5)IrL3][BF4]2 were prepared including the tris(solvent) precursors [(C5Me5)M(acetone)2(H2O)][BF4]2 (M = Rh, Ir) (1a,b). The X-ray molecular structures of 1a,b were determined at low temperature. Complexes 1a,b are isostructural, and both compounds crystallize in the monoclinic space group P2(1)/c with a = 10.157(3) A, b =

  制备了几种新颖的通式[（C5Me5）IrL3] [ ] 2的五甲基环戊二烯基配合物，包括三（溶剂）前体[（C5Me5）M（丙酮）2（H2O）] [ ] 2（M = Rh，Ir） （1a，b）。在低温下确定1a，b的X射线分子结构。配合物1a，b是同构的，两种化合物在单斜空间群P2（1）/ c中均以a = 10.157（3）A，b = 14.038（9）A，c = 16.335（2）A，β= 99.73结晶。 （2）度，对于1a且Z = 4，a = 10.107（9）A，b = 13.994（16）A，c = 15.996（34）A，β= 99.61（12）度，对于Z = 4 1b。配位的水分子氢键合到两个BF4（-）阴离子上。1a，b与吡啶（py）反应得到相关的三（吡啶）配合物[（C5Me5）M（eta1-（N）-py）3] [ ] 2（M = Rh，Ir）（2a，b） 。配合
• Han, Won Seok; Lee, Soon W., Dalton Transactions, 2004, # 10, p. 1656 - 1663
  作者：Han, Won Seok、Lee, Soon W.

  DOI：——

  日期：——