carbon monoxide;dichloromolybdenum;triphenylphosphane | 82443-48-9

• 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;dichloromolybdenum;triphenylphosphane
• CAS: 82443-48-9；17250-39-4
• 化学式: C₃₉H₃₀Cl₂MoO₃P₂
• 分子量: 775.459
• InChiKey: QLZFXXCFKPIGLY-UHFFFAOYSA-L

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：

  carbon monoxide;dichloromolybdenum;triphenylphosphane 、 2,3,11,12-dibenzo-1,4,7,10,13-pentathiatridecane 在 NaOMe 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 以79%的产率得到
  参考文献：
  名称：

  Transition-Metal Complexes with Sulfur Ligands. 113. Syntheses, X-ray Crystal Structures, and Reactivity of Molybdenum(II) Complexes with Thioetherthiolate Ligands Having XS4 Donor Atom Sets (X = S, O, NH)

  摘要：

  In quest of molybdenum complexes that have sulfur donors in their coordination sphere and exhibit reactivity toward small molecules such as CO, NO, NO+, N-3(-), and above all N-2, the chemistry of [Mo(''(R)XS(4)'')] complexes has been investigated. Mo(II) complexes of the type [Mo(CO)(2)(''(R)XS(4)'')] (R = H, X = S, 1a; R = tert-butyl, X = S, 1b; R = H, X = NH, 2; R = H, X = 0, 3) formed by reaction of [Mo(CO)(4)(Cl)(2)] or [Mo(CO)(3)(PPh(3))(2)(Cl)(2)] and the thiols ''(R)XS(4)''-H-2 or corresponding thiolates. Complex la served as a structural reference and proved the Mo center to be seven-coordinate. The [Mo(''S-5'')] fragment approximately forms a square pyramid at the base of which the two cis CO Ligands are coordinated. Crystal data of 1a 0.5Et(2)O: monoclinic space group P2(1)/c; a = 14.182(7) Angstrom, b = 14.525(11) Angstrom, c = 11.421(15) Angstrom beta = 108.98(7)degrees, Z = 4, R/R(w) = 6.0/5.6. The [Mo(''S-5'')] fragment of 1a exhibits the meso-configuration, and NMR spectra indicate the same configuration for the [Mo(''(R)XS(4)'')] fragments of the other CO complexes. Oxidation of 1-3 yielded the C-s symmetrical Mo(IV) oxo complexes [Mo(=O)(''(R)XS(4)'')] (R = H, X = S, 4a; R = tert-butyl, X = S, 4b; R = H, X = NH, 5; R = H, X = 0, 6). Complex 4a was characterized by X-ray structure analysis (orthorhombic space group P2(1)2(1)2(1); a = 10.872(2), b = 14.502(5), c = 11.324(2) Angstrom; Z = 4; R/R(w) = 4.4/3.7%). When treated with PMe(3), 1a, 1b and 2 yielded the thermolabile-phosphine derivatives meso-[Mo(CO)(PMe(3))(''(R)XS(4)'')] (R = H, X = S, 7; R = tert-butyl, X = S, 9; R = H, X = NH, 8) whereas the reaction of 3 gave [Mo(CO)(PMe(3))(2)(''OS4'')] (10). Reaction of 7 with an excess of PMe(3) resulted in cleavage of the bridging S(C2H4)(2) unit from the ''S-5''(2-) ligand and formation of the Mo(IV) complex [Mo(PMe(3))(2)(''S-2'')2] (11). Complex 11 was characterized by X-ray structure analysis (monoclinic space group P2(1)/c, a = 16.857(4) Angstrom, b = 17.742(4) Angstrom, c = 7.569(2) Angstrom, beta = 93.53(2)degrees, Z = 4, R/R(w) = 2.8/2.6) and contains a Mo center surrounded by four S and two cis P donors in a pseudo-trigonal prismatic arrangement. Complexes 1a and 1b reacted with NO+ or NO gas to give the NO complexes [Mo-(NO)(''S-R(5)'')]BF4 (R = H, 12; R = tert-butyl, 13) and [Mo(NO)(2)(''(US5)-U-bu'')] (14). NMR and IR spectra and reactivity suggest that 13 contains dinuclear cations which reversibly dissociate into mononuclear C-1 symmetrical[Mo-(NO)(''S-bu(5)'')](+) ions in solution. Complexes 13 and 14 added PMe(3) or N-3(-) to give [Mo(NO)(PMe(3))(''S-bu(5)'')] (15), [Mo(NO)(N-3)(''S-bu(5)'')] (16) and (NEt(4))[Mo(NO)(2)(N-3)(''S-bu(5)'')] (17). Although all complexes contain small molecules as ligands which are substrates or inhibitors for nitrogenase and 16 and 17 even molecules which theoretically can conproportionate to give N-2, attempts to obtain N-2 complexes with [Mo(''(R)XS(4)'')] fragments remained unsuccessful.

  DOI：

  10.1021/ic00128a006

文献信息

• Molybdenum and tungsten complexes with side-on co-ordinated SPPh₂-ligands. X-Ray crystal structure determination of Mo(CO)₂(PPh₃)(η²-SPPh₂)₂.CH₂Cl₂
  作者：Huub P. M. M. Ambrosius、Jan H. Noordik、Gerry J. A. Ariaans

  DOI：10.1039/c39800000832

  日期：——

  M(CO)3Cl(η5-C5H5) and M(CO)3(PPh3)2Cl2(M = Mo, W) react with SPPh2H and Et3N to give M(CO)2-(η5-C5H5)(η2-SPPh2) and M(CO)2(PPh3)(η2-SPPh2)2, respectively; an X-ray crystal structure determination of Mo(CO)2(PPh3)(SPPh2)2 reveals a 7-co-ordinate pseudopentagonal bipyramidal geometry for the molybdenum atom with an almost planar configuration for the sulphur and phosphorus atoms.

  M(CO)3Cl(δ-5-C5H5)和 M(CO)3(PPh3)2Cl2（M = Mo、W）与 SPPh2H 和 Et3N 反应，分别生成 M(CO)2-(δ-5- )(δ-2-SPPh2)和 M(CO)2(PPh3)(δ-2-SPPh2)2；通过测定 Mo(CO)2(PPh3)(SPPh2)2 的 X 射线晶体结构，发现钼原子具有 7 个配位的假五角双锥几何结构，硫原子和磷原子几乎呈平面构型。
• Molybdenum and tungsten complexes with the heteroallyl-like Ph2P(O)C(S)NR− (R  Me, Ph) as ligand. X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2; A 4 : 3 piano-stool configuration
  作者：H.P.M.M. Ambrosius、W.P. Bosman、J.A. Cras

  DOI：10.1016/s0022-328x(00)80130-8

  日期：1981.7

  Ph2P(O)C(S)N(H)R (R  Me, Ph) reacts with M(CO)3(η5-C5H5)Cl (M  Mo, W) in the presence of Et3N to give M(CO)2(η5-C5H5)(Ph2P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)3(PPh3)2Cl2 (M  Mo, W) reacts with Ph2P(O)C(S)N(H)R (R  Me, Ph) in the presence of Et3N to give complexes in which the central metal atoms are seven

  pH值2 P（O）C（S）N（H）R（RMe中，PH）与M（CO）反应3（η 5 -C 5 H ^ 5）氯（M的Mo，W）中的存在等3 N到得到M（CO）2（η 5 -C 5 H ^ 5）（PH 2 P（O）C（S）NR）。去质子化的配体通过N和S以双齿方式配位，得到四元环系统。M（CO）3（PPh 3）2 Cl 2（MMo，W ）在存在Et 3的情况下与Ph 2 P（O）C（S）N（H）R（RMe，Ph）反应N形成配合物，其中中心金属原子为7个配位体，通过O和S结合的两个配体形成五元环系统，一个PPh 3和两个CO基团。通过元素分析，IR，1 H NMR和31 P NMR光谱以及Mo（CO）2（PPh 3）（Ph 2 P（O）C（S）NPh）的X射线结构分析对复合物进行表征2 ·CH 2 Cl 2。
• Ambrosius; Willemse; Cras, Inorganic Chemistry, 1984, vol. 23, # 17, p. 2672 - 2678
  作者：Ambrosius、Willemse、Cras、Bosman、Noordik

  DOI：——

  日期：——
• Synthesis of Mo(II) and W(II) complexes with 1,1-dithiolate ligands. Improved preparation of W(CO)3(PPh3)2Cl2
  作者：G.J.-J. Chen、R.O. Yelton、J.W. McDonald

  DOI：10.1016/s0020-1693(00)90926-5

  日期：1977.1
• Übergangsmetallkomplexe mit schwefelliganden VI. Synthese der fünf- und sechszähnigen thioetherthiol-liganden dpttd-H2  2,3,11,12-dibenzo-1,4,7,10,13-pentathiatridecan bzw. dhthd-H2  2,3,14,15-dibenzo-1,4,7,10,13,16-hexathiahexadecan sowie ihrer FeII-, Mo0- und MoII-carbonyl-komplexe
  作者：Dieter Sellmann、Ulrich Kleine-Kleffmann

  DOI：10.1016/s0022-328x(00)99277-5

  日期：1983.12