carbon monoxide;molybdenum;7-phenyl-1,4,7-dithiaphosphonane | 147210-31-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: carbon monoxide;molybdenum;7-phenyl-1,4,7-dithiaphosphonane
• CAS: 147210-31-9
• 化学式: C₁₅H₁₇MoO₃PS₂
• 分子量: 436.344
• InChiKey: GOAQGJLQWTUWGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  53.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  carbon monoxide;molybdenum;7-phenyl-1,4,7-dithiaphosphonane 、 溴 以 二氯甲烷 为溶剂， 以67%的产率得到carbon monoxide;molybdenum(2+);7-phenyl-1,4,7-dithiaphosphonane;dibromide
  参考文献：
  名称：

  Template Synthesis and Reactions of Tricarbonylmolybdenum Phosphadithiamacrocycle Complexes

  摘要：

  Treatment of [Me(4)N](2)[PhP(CH2CH2S)(2)] with [Mo(CO)(3)(NCMe)(3)] affords the reactive intermediate [Me(4)N](2)[Mo(CO)(3){PhP(CH2CH2S)(2)}] (1), which undergoes oxidation to afford [Mo{PhP(CH2CH2S)(2)}(2)] (2). Reaction of 1 with a variety of dichloroalkanes produces [Mo(CO)(3){c-PhP(CH2CH2S)(2)X}] (X = CH2CH2, CH2CH2CH2, CH(2)CHMe or CH2CH(OH)CH2). The structure of [Mo(CO)(3){c-PhP(CH2CH2S)(2)CH2CH2}] (3) has been established by X-ray crystallography and consists of a Mo(CO)(3) fragment facially coordinated by the tridentate c-PhP(CH2CH2S)(2)CH2CH2 ligand. Reaction of 3 with bromine affords seven-coordinate [Mo(CO)(2){c-PhP(CH2CH2S)(2)CH2CH2}Br-2] (7), the X-ray crystal structure of which reveals a carbonyl-capped octahedral geometry. Treatment of 3 with sulfur results in loss of the Mo(CO)(3) fragment and is elation of c-PhPS(CH2CH2S)(2)CH2CH2 (8), the X-ray structure of which shows a nine-membered ring with the phosphorus center bearing phenyl and sulfide substituents. Reduction of 8 with sodium naphthalenide affords the parent ligand c-PhP(CH2CH2S)(2)CH2CH2. Crystal data: 2, C20H26MoP2S4, triclinic P (1) over bar, a = 8.105(3) Angstrom, b = 8.263(3) Angstrom, c = 17.663(4) Angstrom, alpha = 100.29(2)degrees, beta = 99.78(2)degrees, gamma = 98.81(2)degrees, Z = 2; 3, C15H17MoO3PS2, monoclinic P2(1)/n, a = 9.600(3) Angstrom, b = 15.594(5) Angstrom, c = 11.335(3) Angstrom, beta = 93.01(2)degrees, Z = 4; 7, C14H17Br2MoO2PS2, monoclinic P2(1)/c, a = 17.039(3) Angstrom, b = 8.686(2) Angstrom, c = 12.466(3) Angstrom, beta = 100.52(2)degrees, Z = 4; 8, C12H17PS3, monoclinic P2(1), a = 6.651(4) Angstrom, b = 7.313(2) Angstrom, c = 14.687(9) Angstrom, beta = 101.62(3)degrees, Z = 2.

  DOI：

  10.1021/ic961143i
• 作为产物：
  描述：

  、 1,2-二氯乙烷 以 乙腈 为溶剂， 以70%的产率得到carbon monoxide;molybdenum;7-phenyl-1,4,7-dithiaphosphonane
  参考文献：
  名称：

  Template Synthesis and Reactions of Tricarbonylmolybdenum Phosphadithiamacrocycle Complexes

  摘要：

  Treatment of [Me(4)N](2)[PhP(CH2CH2S)(2)] with [Mo(CO)(3)(NCMe)(3)] affords the reactive intermediate [Me(4)N](2)[Mo(CO)(3){PhP(CH2CH2S)(2)}] (1), which undergoes oxidation to afford [Mo{PhP(CH2CH2S)(2)}(2)] (2). Reaction of 1 with a variety of dichloroalkanes produces [Mo(CO)(3){c-PhP(CH2CH2S)(2)X}] (X = CH2CH2, CH2CH2CH2, CH(2)CHMe or CH2CH(OH)CH2). The structure of [Mo(CO)(3){c-PhP(CH2CH2S)(2)CH2CH2}] (3) has been established by X-ray crystallography and consists of a Mo(CO)(3) fragment facially coordinated by the tridentate c-PhP(CH2CH2S)(2)CH2CH2 ligand. Reaction of 3 with bromine affords seven-coordinate [Mo(CO)(2){c-PhP(CH2CH2S)(2)CH2CH2}Br-2] (7), the X-ray crystal structure of which reveals a carbonyl-capped octahedral geometry. Treatment of 3 with sulfur results in loss of the Mo(CO)(3) fragment and is elation of c-PhPS(CH2CH2S)(2)CH2CH2 (8), the X-ray structure of which shows a nine-membered ring with the phosphorus center bearing phenyl and sulfide substituents. Reduction of 8 with sodium naphthalenide affords the parent ligand c-PhP(CH2CH2S)(2)CH2CH2. Crystal data: 2, C20H26MoP2S4, triclinic P (1) over bar, a = 8.105(3) Angstrom, b = 8.263(3) Angstrom, c = 17.663(4) Angstrom, alpha = 100.29(2)degrees, beta = 99.78(2)degrees, gamma = 98.81(2)degrees, Z = 2; 3, C15H17MoO3PS2, monoclinic P2(1)/n, a = 9.600(3) Angstrom, b = 15.594(5) Angstrom, c = 11.335(3) Angstrom, beta = 93.01(2)degrees, Z = 4; 7, C14H17Br2MoO2PS2, monoclinic P2(1)/c, a = 17.039(3) Angstrom, b = 8.686(2) Angstrom, c = 12.466(3) Angstrom, beta = 100.52(2)degrees, Z = 4; 8, C12H17PS3, monoclinic P2(1), a = 6.651(4) Angstrom, b = 7.313(2) Angstrom, c = 14.687(9) Angstrom, beta = 101.62(3)degrees, Z = 2.

  DOI：

  10.1021/ic961143i

文献信息

• Tridentate Ligand Effects on Enthalpies of Protonation of (L₃)M(CO)₃ Complexes (M = W, Mo)
  作者：Oltea P. Siclovan、Robert J. Angelici

  DOI：10.1021/ic970670e

  日期：1998.2.1

  enthalpies of protonation (DeltaH(HM)) for the reaction of (L(3))M(CO)(3) complexes, where M = W and Mo and L(3) = cyclic and noncyclic tridentate ligands of the N, S, and P donor atoms, with CF(3)SO(3)H in 1,2-dichloroethane solution at 25 degrees C to give (L(3))M(CO)(3)(H)(+)CF(3)SO(3)(-). The basicities (-DeltaH(HM)) increase with the ligand donor groups (X, Y, or Z) in the order S

  滴定量热法已用于确定（L（3））M（CO）（3）配合物反应的质子化焓（DeltaH（HM）），其中M = W和Mo且L（3）=环状和N，S和P供体原子的非环状三齿配体，与CF（3）SO（3）H在1,2-二氯乙烷溶液中于25°C加热，得到（L（3））M（CO）（3） （H）（+）CF（3）SO（3）（-）。碱度（-DeltaH（HM））随着配体供体基团（X，Y或Z）的顺序增加S
• Copper and nickel complexes of the new phosphadithiamacrocycle 1-phenyl-1-phospha-4,7-dithiacyclononane
  作者：Raymond J. Smith、Anne K. Powell、Neil Barnard、Jonathan R. Dilworth、Philip J. Blower

  DOI：10.1039/c39930000054

  日期：——

  The novel cyclic ligand 1-phenyl-1-phospha-4-7-dithiacyclononane forms highly stable transition metal and d10 metal complexes; the X-ray structure of the tetrahedral copper(I) complex shows the ligand to be capable of both facial tridentate coordination and monodentate coordination, and the nickel(II) complex is easily and reversibly converted electrochemically to nickel(I) and nickel(III) complexes.

  新型环状配体 1-苯基-1-磷杂-4-7-二硫杂环壬烷可形成高度稳定的过渡金属和 d10 金属配合物；四面体铜（I）配合物的 X 射线结构显示，该配体既能进行面三齿配位，也能进行单齿配位，而且镍（II）配合物在电化学作用下很容易可逆地转化为镍（I）和镍（III）配合物。