[PhTttBu]Ni(I)CO | 326868-98-8

• 英文名称: [PhTttBu]Ni(I)CO
• 英文别名: (phenyltris((tert-butylthio)methyl)borate)carbonylnickel；[PhTt^tBu]Ni^(I)CO；(phenyl(tris((tert-butylmethyl)thio)methyl)borate)Ni(CO)；[(phenyl-tris((tert-butylthio)methyl)borate)NiCO]；[phenyltris((tert-butylthio)methyl)borate]Ni(I)CO；(phenyltris((tert-butylthio)methyl)borate)Ni(CO)；[PhTt(tBu)]Ni(I)CO
• CAS: 326868-98-8
• 化学式: C₂₂H₃₈BNiOS₃
• 分子量: 484.242
• InChiKey: XKWSLRQSHDWUTN-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：

  [PhTttBu]Ni(I)CO 、 以 四氢呋喃 为溶剂， 生成 [(CH(C(CH3)NC6H3(CH(CH3)2)2)2bis(μ-(18)oxo)copper(III)nickel(III)(phenyltris((tert-butylthio)methyl)borate)]
  参考文献：
  名称：

  Mixed metal bis(μ-oxo) complexes with [CuM(μ-O)₂]ⁿ⁺(M = Ni(iii) or Pd(ii)) cores

  摘要：

  通过将单核过氧物种与还原型金属前体在±80 °C下结合，制备出了两种高活性异核双（δ-氧）配合物，并通过紫外-可见光、EPR/NMR和共振拉曼光谱对其进行了鉴定，同时通过密度泛函计算对铜钯体系进行了确证。

  DOI：

  10.1039/b404640d
• 作为产物：
  描述：

  [phenyltris((tert-butylthio)methyl)borate]NiCl 、 一氧化碳 在 CH₃Li 作用下， 以 乙醚 为溶剂， 以51%的产率得到[PhTttBu]Ni(I)CO
  参考文献：
  名称：

  Ni（+）-CO模型配合物的光谱和计算研究：对乙酰-CoA合酶催化机制的影响。

  摘要：

  四坐标Ni（+）络合物[PhTt（t）（Bu）] Ni（I）CO，其中PhTt（t）（）（Bu）=苯基三（（叔丁基硫代甲基）甲基）硼酸酯（三齿硫醚供体）配体）作为乙酰辅酶A合酶（ACS）催化循环中关键Ni-CO反应中间体的可能模型。共振拉曼，电子吸收，磁圆二向色性（MCD），变温变场MCD和电子顺磁共振波谱与密度泛函理论和半经验INDO / S-CI计算结合使用，以研究电子的基态和激发态。 [PhTt（t）（）（Bu）] Ni（I）CO。这些研究揭示了广泛的Ni（+）-> CO pi背键相互作用，如低CO拉伸频率（1995 cm（-）（1）），计算出的CO拉伸力常数为15.5 mdyn / A（与k（CO）（游离CO）= 18.7 mdyn / A）相比，Ni（+）-> CO电荷转移吸收强度高。计算表明，这种高度的pi反向键合是由于Ni（+）3d轨道在能量上与CO pi受体轨道非常接近。在

  DOI：

  10.1021/ic020441e

文献信息

• New Synthetic Routes to a Disulfidodinickel(II) Complex: Characterization and Reactivity of a Ni₂(µ-η²:η²-S₂) Core
  作者：Jaeheung Cho、Katherine M. Van Heuvelen、Glenn P. A. Yap、Thomas C. Brunold、Charles G. Riordan

  DOI：10.1021/ic800321x

  日期：2008.5.19

  Activation of elemental sulfur by the monovalent nickel complex [PhTt (tBu)]Ni(CO) [PhTt(tBu)=phenyltris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt (tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S2 ligand that fosters

  单价镍络合物[PhTt（tBu）] Ni（CO）[PhTt（tBu）=苯基三（（叔丁基甲基）硫代]甲基}硼酸酯]活化元素硫，生成二硫代二镍（II）络合物2。可通过[PhTt（tBu）] Ni（SCPh3）的热分解来访问这些物种。光谱，磁性和X射线衍射研究确定2包含mu-eta（2）：eta（2）-S2配体，可促进Ni（II）离子之间的反铁磁交换耦合。该观察结果与较轻的同类物氧气形成鲜明对比，后者更有利于双（mu-oxo）dinickel（III）结构。2将PPh 3氧化为SPPh3并与O2反应，生成了几种产物，其中一种已被鉴定为[（PhTt（tBu））Ni] 2（mu-S）（3）。
• Dioxygen Activation by a Nickel Thioether Complex:  Characterization of a Ni^III₂(μ-O)₂ Core
  作者：Beaven S. Mandimutsira、Jennifer L. Yamarik、Thomas C. Brunold、Weiwei Gu、Stephen P. Cramer、Charles G. Riordan

  DOI：10.1021/ja016209+

  日期：2001.9.1

  The activation of dioxygen by nickel complexes may be considered to proceed via several distinct pathways. While disulfide formation from outer sphere electron transfer is the most common result of oxygen sensitivity in nickel thiolato complexes, certain derivatives generate sulfur oxygenates with maintenance of the coordination sphere. In the thoroughly studied cisdiaminodithiolato complex Ni(BME-DACO)

  镍络合物对分子氧的活化可以被认为是通过几种不同的途径进行的。虽然由外球电子转移形成的二硫化物是镍硫醇合络合物中氧敏感性的最常见结果，但某些衍生物会生成含硫的含氧化合物，并保持配位球。在深入研究的顺二氨基二硫醇络合物 Ni(BME-DACO) 中，1 Darensbourg 详细介绍了金属砜和金属亚砜的形成机制。2 硫醇硫是亲核性最高的位点，这一观察得到了从头算计算的支持，显示硫 p 轨道为 HOMO。3
• Organometallic Cobalt(II) and Nickel(II) Complexes Supported by Thioether Ligation:  Unexpected Nickel Alkylation by the Borato Ligand Phenyltris((<i>tert</i>-butylthio)methyl)borate
  作者：Peter J. Schebler、Beaven S. Mandimutsira、Charles G. Riordan、Louise M. Liable-Sands、Christopher D. Incarvito、Arnold L. Rheingold

  DOI：10.1021/ja002638g

  日期：2001.1.1
• A Monomeric Nickel−Dioxygen Adduct Derived from a Nickel(I) Complex and O₂
  作者：Koyu Fujita、Ralph Schenker、Weiwei Gu、Thomas C. Brunold、Stephen P. Cramer、Charles G. Riordan

  DOI：10.1021/ic049876n

  日期：2004.5.1

  The nickel(I) complex [PhTt(Ad)]Ni(CO) (PhTt(Ad), phenyltris((1-adamantylthio)methyl)borate) reacts with O-2 generating a 1:1 species identified as a side-on dioxygen adduct based on its spectroscopic properties as supported by DFT computational results and by its reactivity. The Ni EXAFS data are fit to a S3O2 coordination environment with short Ni-O distances, 1.85 Angstrom. The brown complex displays a rhombic EPR signal with g values of 2.24, 2.19, 2.01. DFT and INDO/S-Cl computations replicate the EXAFS and EPR features and suggest that 2 is a side-on [NiO2](+) complex with geometric and electronic properties that are best rationalized in terms of a highly covalent Ni(II)-superoxo description. [PhTt(Ad)]-Ni(O-2) oxidizes PPh3 to OPPh3, NO to NO3-, and [PhTt(tBu)]Ni(CO) to the nonsymmetric [PhTt(Ad)]Ni(mu-O)(2)Ni[PhTt(tBu)] dimer.
• Spectroscopic and Computational Studies on [(PhTt^{^<i>t</i>}^Bu)₂Ni₂(μ-O)₂]:  Nature of the Bis-μ-oxo (Ni³⁺)₂ “Diamond” Core
  作者：Ralph Schenker、Beaven S. Mandimutsira、Charles G. Riordan、Thomas C. Brunold

  DOI：10.1021/ja027049k

  日期：2002.11.1

  Spectroscopic and density functional theory (DFT) electronic structure computational studies on a binuclear bis-mu-oxo bridged (Ni3+)(2) complex, [(PhTt(tBu))(2)Ni-2(mu-O)(2)] (1), where (PhTt(tBu)) represents phenyltris((tert-butylthio)methyl) borate, are presented and discussed. These studies afford a detailed description of the Ni2O2 core electronic structure in bis-mu-oxo (Ni3+)(2) dimers and provide insight into the possible role of the (PhTtBu) thioether ligand in the formation of 1 from a Ni1+ precursor by O-2 activation. From a normal coordinate analysis of resonance Raman data, a value of k(NI-O) = 2.64 mdyn/Angstrom is obtained for the Ni-O stretch force constant for 1. This value is smaller than k(cu-O) = 2.82-2.90 mdyn/Angstrom obtained for bis-mu-oxo (Cu3+)(2) dimers possessing nitrogen donor ligands, indicating a reduced metal-oxo bond strength in 1. Electronic absorption and magnetic circular dichroism spectroscopic techniques permit identification of several O-->Ni and S-->Ni charge transfer (CT) transitions that are assigned on the basis of DFT calculations. The dominant O-Ni CT transition of 1 occurs at 17 700 cm(-1), red-shifted by similar to7000 cm-1 relative to the corresponding transition in bis-mu-oxo (Ni3+)(2) dimers with nitrogen donor ligands. This red-shift along with the relatively low value of k(Ni-O) are due primarily to the presence of the thioether ligands in 1 that greatly affect the compositions of the Ni2O2 core MOs. This unique property of the thioether ligand likely contributes to the reactivity of the Ni center in the precursor [(PhTtBu)Ni1+CO] toward O-2. DFT computations reveal that conversion of a hypothetical side-on peroxo (Ni2+)(2) dimer, [(PhTtBu)(2)Ni-2(mu-eta(2):eta(2)-O-2)], to the bis-mu-oxo (Ni3+)(2) dimer 1 is energetically favorable by 32 kcal/mol and occurs without a significant activation energy barrier (DeltaH(double dagger) = 2 kcal/mol).