MoOCl(N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine(2-)) | 109309-13-9

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: MoOCl(N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine(2-))
• CAS: 109309-13-9
• 化学式: C₁₆H₁₈ClMoN₂OS₂
• 分子量: 449.857
• InChiKey: SJJHVMBHQMYXQU-UHFFFAOYSA-K

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：

  sodium phenoxide 、 MoOCl(N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine(2-)) 以 四氢呋喃 为溶剂， 以45%的产率得到cis,trans-MoO(OPh)(N,N'-dimethyl-N,N'-bis(2-thiolatophenyl)ethylenediamine)
  参考文献：
  名称：

  Mononuclear and Binuclear Molybdenum(V) Complexes of the Ligand N,N‘-Dimethyl-N,N‘-bis(2-mercaptophenyl)ethylenediamine:  Geometric Isomers

  摘要：

  The syntheses of mononuclear complexes cis-Mo(V)OXL (X = Cl, Br, OMe, OEt, OPh, SPh, NCS, OSiMe(3)) and two binuclear complexes Mo(2)(V)O(3)L(2) of the title ligand LH(2) are reported. Two forms of MoOCIL, with cis oxo and chloro ligands, were crystallized, one in space group P2(1)/n, with a 10.440(2) Angstrom, b = 14.260(2) Angstrom, 12.041(2) Angstrom, beta = 102.76(2)degrees, V = 1748(1) Angstrom(3), and Z = 4, and the other in P2(1)/n, with a = 13.564(4) Angstrom, b = 7.172(2) Angstrom, c = 18.242(6) Angstrom, beta = 95.19(1)degrees, V = 1767(2) Angstrom(3), and Z = 4. MoO(OSiMe(3))L crystallizes in space group P2(1)/c, with a = 15.923(3) Angstrom, b = 11.141(2) Angstrom, c = 14.186(2) Angstrom, beta = 112.64(2)degrees, V = 2323(1) Angstrom(3), and Z = 4, while MoO(NCS)L crystallizes in Pna2(1), with a = 22.471(2) Angstrom, b = 12.136(2) Angstrom, c = 7.138(1) Angstrom, V = 1947(1) Angstrom(3), and Z = 4. The four structures reveal two possible conformations for ligand L: one with trans S atoms (cis,trans-MoOCIL and -MoO(OSiMe(3))L) and one with cis S atoms (cis,cis-MoOCIL and -MoO(NCS)L). The cis, cis isomers are converted to the cis,trans forms under reflux in MeCN at 80 degrees C. Only the cis,trans forms could be isolated for bulkier ligands X (OPh, SPh, OSiMe(3)). A short H3C ... X interaction is present in the cis,cis forms: C ... Cl = 3.07 Angstrom and C ... N = 2.93 Angstrom, for X = Cl and NCS, respectively. Infrared and electronic spectral data provide unambiguous identification of the stereochemistry of ligand L in mononuclear complexes MoOXL. Effective removal of ligand X = OR from cis,cis-MoO(OR)L (R = Me, Et) led to two binuclear complexes (Mo(V)OL)(2)(mu-O) of C-i and C-1 point symmetries. C-i-(MoOL)(2)(mu-O). thf crystallizes in space group P2(1)/c, with a = 8.5650(5) Angstrom, b = 15.1862(9) Angstrom, c = 16.8038(9) Angstrom, beta = 100.183(1)Alpha, V = 2157.1(8) Angstrom(3), and Z = 2, while C-1-(MoOL)(2)(mu-O). CH2Cl2 crystallizes in space group P2(1)/c, with a = 12.5250(5) Angstrom, b = 24.673(1) Angstrom, c = 12.7253(6) Angstrom, beta = 108.070(4)degrees, V = 3738.6(3) Angstrom(3), and Z = 4. C-i-(MoOL)(2)(mu-O). thf features two cis,trans-Mo(V)OXL centers with X = mu-O, while C-1-(MoOL)(2)(mu-O). CH2Cl2 contains a cis,trapls and a cis,cis center. In the latter, the Mo-O-Mo link is asymmetric, allowing relief of steric crowding on the cis,cis side of the molecule.

  DOI：

  10.1021/ic960848h
• 作为产物：
  描述：

  cis,trans-Mo(VI)O2(N,N'-dimethyl-N,N'-bis(2-thiolatophenyl)ethylenediamine) 以 乙腈 为溶剂， 以67%的产率得到MoOCl(N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine(2-))
  参考文献：
  名称：

  Mononuclear and Binuclear Molybdenum(V) Complexes of the Ligand N,N‘-Dimethyl-N,N‘-bis(2-mercaptophenyl)ethylenediamine:  Geometric Isomers

  摘要：

  The syntheses of mononuclear complexes cis-Mo(V)OXL (X = Cl, Br, OMe, OEt, OPh, SPh, NCS, OSiMe(3)) and two binuclear complexes Mo(2)(V)O(3)L(2) of the title ligand LH(2) are reported. Two forms of MoOCIL, with cis oxo and chloro ligands, were crystallized, one in space group P2(1)/n, with a 10.440(2) Angstrom, b = 14.260(2) Angstrom, 12.041(2) Angstrom, beta = 102.76(2)degrees, V = 1748(1) Angstrom(3), and Z = 4, and the other in P2(1)/n, with a = 13.564(4) Angstrom, b = 7.172(2) Angstrom, c = 18.242(6) Angstrom, beta = 95.19(1)degrees, V = 1767(2) Angstrom(3), and Z = 4. MoO(OSiMe(3))L crystallizes in space group P2(1)/c, with a = 15.923(3) Angstrom, b = 11.141(2) Angstrom, c = 14.186(2) Angstrom, beta = 112.64(2)degrees, V = 2323(1) Angstrom(3), and Z = 4, while MoO(NCS)L crystallizes in Pna2(1), with a = 22.471(2) Angstrom, b = 12.136(2) Angstrom, c = 7.138(1) Angstrom, V = 1947(1) Angstrom(3), and Z = 4. The four structures reveal two possible conformations for ligand L: one with trans S atoms (cis,trans-MoOCIL and -MoO(OSiMe(3))L) and one with cis S atoms (cis,cis-MoOCIL and -MoO(NCS)L). The cis, cis isomers are converted to the cis,trans forms under reflux in MeCN at 80 degrees C. Only the cis,trans forms could be isolated for bulkier ligands X (OPh, SPh, OSiMe(3)). A short H3C ... X interaction is present in the cis,cis forms: C ... Cl = 3.07 Angstrom and C ... N = 2.93 Angstrom, for X = Cl and NCS, respectively. Infrared and electronic spectral data provide unambiguous identification of the stereochemistry of ligand L in mononuclear complexes MoOXL. Effective removal of ligand X = OR from cis,cis-MoO(OR)L (R = Me, Et) led to two binuclear complexes (Mo(V)OL)(2)(mu-O) of C-i and C-1 point symmetries. C-i-(MoOL)(2)(mu-O). thf crystallizes in space group P2(1)/c, with a = 8.5650(5) Angstrom, b = 15.1862(9) Angstrom, c = 16.8038(9) Angstrom, beta = 100.183(1)Alpha, V = 2157.1(8) Angstrom(3), and Z = 2, while C-1-(MoOL)(2)(mu-O). CH2Cl2 crystallizes in space group P2(1)/c, with a = 12.5250(5) Angstrom, b = 24.673(1) Angstrom, c = 12.7253(6) Angstrom, beta = 108.070(4)degrees, V = 3738.6(3) Angstrom(3), and Z = 4. C-i-(MoOL)(2)(mu-O). thf features two cis,trans-Mo(V)OXL centers with X = mu-O, while C-1-(MoOL)(2)(mu-O). CH2Cl2 contains a cis,trapls and a cis,cis center. In the latter, the Mo-O-Mo link is asymmetric, allowing relief of steric crowding on the cis,cis side of the molecule.

  DOI：

  10.1021/ic960848h

文献信息

• Analogues for the Molybdenum Center of Sulfite Oxidase:  Oxomolybdenum(V) Complexes with Three Thiolate Sulfur Donor Atoms
  作者：M. L. Mader、Michael D. Carducci、John H. Enemark

  DOI：10.1021/ic990768o

  日期：2000.2.1

  cis,trans-(L-N2S2)Mo(V)O(SR) [L-N2S2H2 = N,N'-dimethyl-N,N'-bis(mercaptophenyl)ethylenediamine; R = CH2Ph, CH2CH3, and p-C6H4-Y (Y = CF3, Cl, Br, F, H, CH3, CH2CH3, and OCH3)] are the first structurally characterized mononuclear Mo compounds with three thiolate donors, as occurs at the Mo active site in sulfite oxidase. X-ray crystal structures of the cis,trans-(L-N2S2)Mo(V)O(SR) compounds, where R

  顺式，反式-（L-N 2 S 2）Mo（V）O（SR）[L-N 2 S 2 H 2 ＝ N，N'-二甲基-N，N'-双（巯基苯基）乙二胺；R = CH2Ph，CH2 和p-C6H4-Y（Y = CF3，Cl，Br，F，H，CH3，CH2 和O ）]是第一个具有三个硫醇盐供体的结构特征的单核Mo化合物，亚硫酸盐氧化酶中的Mo活性位。顺式，反式-（L-N2S2）Mo（V）O（SR）化合物的X射线晶体结构显示相似的配位关系，其中R = CH2Ph，CH2 ，p- -O 和p- - 赤道平面上具有所有三个硫醇盐供体的Mo原子的几何构型。这种配位几何结构使两个相邻的S ppi轨道平行于Mo = O键，类似于亚硫酸盐氧化酶中ene-dithiolate配体的取向。第三个S ppi轨道位于赤道平面。从S p到Mo d轨道的电荷转移跃迁发生在大约28,000 cm（-1）（epsilon：4
• Molybdenum(VI) and molybdenum(V) complexes with N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine. Electrochemical and electron paramagnetic resonance models for the molybdenum(VI/V) centers of the molybdenum hydroxylases and related enzymes
  作者：Dulal Dowerah、Jack T. Spence、Raghuvir Singh、Anthony G. Wedd、Graham L. Wilson、Frank Farchione、John H. Enemark、John Kristofzski、Michael Bruck

  DOI：10.1021/ja00253a016

  日期：1987.9