fac-[Re(κ3-H(μ-H)B(2-mercapto-1-methylimidazole-H))2(CO)3] | 315229-29-9

• 英文名称: fac-[Re(κ3-H(μ-H)B(2-mercapto-1-methylimidazole-H))2(CO)3]
• 英文别名: [Re(κ3-H(μ-H)B(2-mercapto-1-methylimidazolyl)2)(CO)3]；Re(I)[κ3-H(μ-H)B(2-mercapto-1-methylimidazolyl)2](CO)3
• CAS: 315229-29-9
• 化学式: C₁₁H₁₂BN₄O₃ReS₂
• 分子量: 509.391
• InChiKey: OZXUBIBBJOHPLM-UHFFFAOYSA-N

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：

  fac-[Re(κ3-H(μ-H)B(2-mercapto-1-methylimidazole-H))2(CO)3] 、 乙二胺 以 甲醇 为溶剂， 以63%的产率得到
  参考文献：
  名称：

  Reactivity of [Re{κ³-H(μ-H)B(tim^Me)₂}(CO)₃] (tim^Me = 2-Mercapto-1-methylimidazolyl) toward Neutral Substrates

  摘要：

  The complex [Re{kappa(3)-H(mu-H)B(tim(Me))(2)}(CO)(3)] (2a) (tim(Me) = 2-rnercapto-1-methylimidazolyl) reacts with a variety of neutral substrates to afford new complexes featuring the dihydrobis(2-mercapto-1-methylimidazolyl)borate coordinated in a bidentate or unidentate fashion. By treating 2a with unidentate ligands, the mononuclear complexes [Re{kappa(2)-H2B(tim(Me))2}(CO)(3)(L)] (L = imidazole (5), 4-(dimethylamino)pyridine (6), tert-butylisonitrile (7), triphenylphosphine (8)) were formed, upon replacement of the agostic B-H...Re bond by the correspondent unidentate ligand. With potentially bidentate substrates, 2a is transformed into mononuclear or dinuclear complexes, depending on the atom donor set of the reacting substrates. Reaction of compound 2a with ethylenediamine (en) gave the complex [Re{kappa(1)-H2B(tim(Me))(2)}(CO)(3)(en)] (9), because of cleavage of the agostic interaction, dechelation of one mercaptoimidazolyl ring, and bidentate coordination of the amine. By contrast, 1,2-bis(diphenyl)phosphinoethane (dppe) is not able to replace the mercaptoimidazolyl ring, and the dimer [Re{kappa(2)-H2B(tim(Me))(2)}(CO)(3)](2)(mu-dppe) (10) was formed. The novel Re(l) tricarbonyl complexes (5-10) have been fully characterized, including by X-ray diffraction analysis in the case of 6, 8, 9, and 10. The X-ray diffraction study confirmed the unprecedented unidentate coordination mode of the dihydrobis(2-mercapto-1-methylimidazolyl)borate in complex 9.

  DOI：

  10.1021/ic011171n
• 作为产物：
  描述：

  Re(CO)3(CH₃C₃H₂N₂S)2BH₂(C₃H₄N₂) 以 not given 为溶剂， 生成 fac-[Re(κ3-H(μ-H)B(2-mercapto-1-methylimidazole-H))2(CO)3]
  参考文献：
  名称：

  Reactivity of [Re{κ³-H(μ-H)B(tim^Me)₂}(CO)₃] (tim^Me = 2-Mercapto-1-methylimidazolyl) toward Neutral Substrates

  摘要：

  The complex [Re{kappa(3)-H(mu-H)B(tim(Me))(2)}(CO)(3)] (2a) (tim(Me) = 2-rnercapto-1-methylimidazolyl) reacts with a variety of neutral substrates to afford new complexes featuring the dihydrobis(2-mercapto-1-methylimidazolyl)borate coordinated in a bidentate or unidentate fashion. By treating 2a with unidentate ligands, the mononuclear complexes [Re{kappa(2)-H2B(tim(Me))2}(CO)(3)(L)] (L = imidazole (5), 4-(dimethylamino)pyridine (6), tert-butylisonitrile (7), triphenylphosphine (8)) were formed, upon replacement of the agostic B-H...Re bond by the correspondent unidentate ligand. With potentially bidentate substrates, 2a is transformed into mononuclear or dinuclear complexes, depending on the atom donor set of the reacting substrates. Reaction of compound 2a with ethylenediamine (en) gave the complex [Re{kappa(1)-H2B(tim(Me))(2)}(CO)(3)(en)] (9), because of cleavage of the agostic interaction, dechelation of one mercaptoimidazolyl ring, and bidentate coordination of the amine. By contrast, 1,2-bis(diphenyl)phosphinoethane (dppe) is not able to replace the mercaptoimidazolyl ring, and the dimer [Re{kappa(2)-H2B(tim(Me))(2)}(CO)(3)](2)(mu-dppe) (10) was formed. The novel Re(l) tricarbonyl complexes (5-10) have been fully characterized, including by X-ray diffraction analysis in the case of 6, 8, 9, and 10. The X-ray diffraction study confirmed the unprecedented unidentate coordination mode of the dihydrobis(2-mercapto-1-methylimidazolyl)borate in complex 9.

  DOI：

  10.1021/ic011171n

文献信息

• Re and Tc Complexes Containing B−H···M Agostic Interactions as Building Blocks for the Design of Radiopharmaceuticals
  作者：Raquel Garcia、António Paulo、Ângela Domingos、Isabel Santos、Kirstin Ortner、Roger Alberto

  DOI：10.1021/ja002652t

  日期：2000.11.1
• Disruption of Unprecedented B‐H…M Agostic Interactions: An Alternative Approach for Labeling Bioactive Molecules
  作者：R. Garcia、A. Paulo、A. Domingos、I. Santos、H.‐J. Pietzsch

  DOI：10.1081/sim-200047542

  日期：2005.1.1

  The agostic B-H...Re bond in complexes [Rekappa(3)-R(mu H)B(tim(Me))(2)}(CO)(3)] (R= H (1), Ph (2), tim(Me) = 2-mercapto-1-methylimidazolyl) is readily cleaved by t-butylisonitrile or cyclohexylisonitrile leading to the mixed-ligand complexes [Rekappa(2)-Ph(mu-H)B(tim(Me))(2)}(C equivalent to (NBu)-Bu-t)(CO)(3)] (3) and [Rekappa(2)-H(mu-H)B(tim(Me))(2)}(C equivalent to N-cyclohexyl)(CO)(3)] (4), respectively. Bearing in mind the so-called [2 + 1] mixed ligand approach for the development of target-pecific radiopharmaceuticals, reactions of 1 with isonitriles carrying the (2-methoxyphenyl)piperazine pharmacophore (part of WAY 100635) were also studied and the complexes [Rekappa(2)-H(mu-H)B(tim(Me))(2)}(C equivalent to N-R'-WAY)(CO)(3)] (R' = butylene (5), pentylene (6) or hexylene (7)) isolated. The novel mixed Re(I) tricarbonyl complexes (3-7) have been characterized by the usual analytical techniques, which included X-ray diffraction analysis in the cases of 3, 4 and 5. The affinity of the complexes 5-7 toward the 5-HT1A receptors was tested in competitive receptor binding assays and the IC50 values found were in the 21.9-66.5 nM range. Complex 7, with the longest spacer length between the isonitrile function and the pharmacophore, has shown an improved selectivity towards the 5-HT1A subtype of receptors when compared with 5 and 6.
• Rhenium(I) Tricarbonyl Complexes with Poly(azolyl)borates Generated in Situ from an Organometallic Precursor Containing the B−H···Re Coordination Motif
  作者：Margarida Videira、Carolina Moura、Amitabha Datta、António Paulo、Isabel C. Santos、I. Santos

  DOI：10.1021/ic802403u

  日期：2009.5.4

  Complex fac-[Re(kappa(3)-H(mu-H)(2)B(tim(Me)))(CO)(3)] (1) reacts with protic azoles, like 2-mercapto-1-methylimidazole (timM(8)H), 2-mercaptobenzothiazole (bztH), or pyrazoles (pz*H), to afford fac-[Re(kappa(3)-H(mu-H)B(tim(Me))(2)(CO)(3)] (2), fac-[Re(kappa(3)- H(mu-H)B(tim(Me))(bzt))(CO)(3)] (3), fac-[Re(kappa(3)-H(mu-H)B(tim(Me))(pz))(CO)(3)] (4), fac-[Re(kappa(3)-HB(tim(Me))(pz)(2))(CO)(3)] (5), and fac- [Re(kappa(3)-H(mu-H)B(tim(Me))(3,5-Me-2-4-EtOOCCH(2)pz))(CO)(3)] (6). Complexes 2- 6 are stabilized by tridentate poly(azolyl)borates generated in situ, and their formation involves most probably a metal-assisted process which is considerably faster for the pyrazole derivatives. The characterization of the novel complexes, 3-6, has been done by common analytical techniques, including single crystal X-ray diffraction analysis. The solid state structures confirmed the presence of hybrid heteroscopionates, presenting (kappa(3)-H, S, S'), (kappa(3)-H, S, N), or (kappa(3)-S, N, N) binding motifs. Multinuclear (H-1, C-13, and B-11) NMR studies have also shown that the coordination mode found in the solid state is retained in solution.