(CO)5W(η(1)-bis(diphenylphosphino)methane) | 35324-78-8

• 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: (CO)5W(η(1)-bis(diphenylphosphino)methane)
• 英文别名: W(CO)5(η(1)-bis(diphenylphosphino)methane)；W(CO)5(bis-(diphenylphosphino)-methane)；(CO)5W(η(1)-PPh2CH2PPh2)；[W(CO)5(η1-bis(diphenylphosphino)methane)]；Carbon monoxide;diphenylphosphanylmethyl(diphenyl)phosphane;tungsten
• CAS: 35324-78-8
• 化学式: C₃₀H₂₂O₅P₂W
• 分子量: 708.299
• InChiKey: DZPDZRANXDWCBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  38
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (CO)5W(η(1)-bis(diphenylphosphino)methane) 以 氘代苯 为溶剂， 以0%的产率得到tetracarbonyl-bis(diphenylphosphino)methane-tungsten(0)
  参考文献：
  名称：

  On the synthesis and 31P{1H} NMR spectrum of (CO) 5W(μ-PPh2CH2PPh2) W(CO)5

  摘要：

  The dimetallic complex, (CO)(5)W(mu-PPh(2)CH(2)PPh(2))W(CO)(5), is synthesized from either a 2:1 mixture of (CO)(5)W(NCMe) and (CO)(5)W(eta(1)-PPh(2)CH(2)PPh(2)) or a 3:1 mixture of (CO)(5)W(NCMe) and PPh(2)CH(2)PPh(2) in toluene at 60 degrees C. The coupling constants, (2)J(PP') = 22.9 Hz, (1)J(WP) = 246.9 Hz and (3)J(WP') = 4.5 Hz are consistent with those reported in the literature for similar complexes. The complex (CO)(5)W(eta(1)-PPh(2)CH(2)PPh(2)) is stable with respect to chelation at room temperature.

  DOI：

  10.1016/0022-328x(94)05384-n
• 作为产物：
  描述：

  W(CO)5(Ph2PCH2PPh2H)CF3SO3 在 1,3-diphenylguanidine 作用下， 以 二氯甲烷 为溶剂， 以>99的产率得到(CO)5W(η(1)-bis(diphenylphosphino)methane)
  参考文献：
  名称：

  Rottink, Mary K.; Angelici, Robert J., Inorganic Chemistry, 1993, vol. 32, # 11, p. 2421 - 2425

  摘要：

  DOI：

文献信息

• Catalysed and uncatalysed substitution reactions of [W(CO)5(NCR)] (R = Me, Et)
  作者：Cheryl-Ann Dickson、Anne W. McFarlane、Neil J. Coville

  DOI：10.1016/s0020-1693(00)80834-8

  日期：1989.4

  Abstract The reaction between [W(CO)5(NCR)] (R = Me, Et) and tBuNC in the presence of PdO yielded both [W(CO)4(CNBut)2] and [W(CO)4(NCR)(CNBut)] and revealed that both RCN and CO are catalytically replaced by tBuNC. Reaction of a 2:1 mixture of [W(CO)5(NCMe)] and PPh2(CH2)nPPh2 (P-P; n = 2, 5) in toluene at 55 °C gave a product mixture consisting of the bridged complex [W(CO)5(P-P)W(CO)5] (dominant product)

  摘要[W（CO）5（NCR）]（R = Me，Et）与tBuNC在PdO存在下的反应产生了[W（CO）4（CNBut）2]和[W（CO）4（NCR） ）（CNBut）]，并发现RCN和CO均被tBuNC催化取代。[W（CO）5（NCMe）]与PPh2（CH2）nPPh2（PP; n = 2，5）的2：1混合物在甲苯中于55°C反应，得到由桥联配合物[W]组成的产物混合物（CO）5（PP）W（CO）5]（主要产物）和螯合物[W（CO）4（PP）]。出乎意料的是，当与PPh2（ ）nPPh2（n = 4，5）的反应在CHCl3中进行时，螯合物[W（CO）4（PP）]是主要产物。
• Thiosemicarbazone platinacycles with tertiary phosphines. Preparation of novel heterodinuclear platinum–tungsten complexes
  作者：Darío Lata、M. Teresa Pereira、Juan M. Ortigueira、Javier Martínez、Brais Bermúdez、Jesús J. Fernández、José M. Vila

  DOI：10.1016/j.poly.2012.04.015

  日期：2012.6

  afforded the tetranuclear platinum(II) compounds [Pt(R1C6H3)C(H) NN C(S)NHR2}]4 (1a–1f) with the ligand as terdentate [C,N,S] after C–H activation and NH deprotonation. The reaction of 1a–1f with PPh3 in 1:4 M ratio gave the mononuclear compounds [Pt(R1C6H3)C(H) NN C(S)NHR2}(PPh3)] (2a–2f). Treatment of 1a–1f with large-bite diphosphines Ph2P(CH2)nPPh2 (n = 2, dppe; n = 3, dppp; n = 4, dppb) afforded the

  硫代半咔唑（R1C6H4）C（H）NN（H）C（S）NHR2的抽象处理[R1，R2：4-Me，H（a）; 4-Me，Me（b）; 4-Me，Et（c）; 2-Me，H（d）; 2-Me，Me（e）; 2-Me，Et（f）]与顺式[PtMe2（cod）]提供四核铂（II）化合物[Pt （（R1C6H3）C（H）NN C（S）NHR2}] 4（1a-1f） C–H活化和NH去质子化后，配体为齿状[C，N，S]。1a-1f与PPh3以1：4 M的比例反应生成单核化合物[Pt （（R1C6H3）C（H）NN C（S）NHR2}（PPh3）]（2a-2f）。用大剂量二膦Ph2P（CH2）nPPh2（n = 2，dppe; n = 3，dppp; n = 4，dppb）处理1a-1f得到双核化合物[Pt [（R1C6H3）C（H）N –N = C（S）NHR2]} 2 μ-Ph2P（ ）n
• Cycloplatination of Thiosemicarbazones Derived from Furane. Crystal and Molecular Structure of [{Pt[(OC4H2)C(Me)=NN=C(S)NHEt]}2{μ-Ph2P(CH2)2PPh2}]
  作者：Luis Adrio、José M. Antelo、Juan M. Ortigueira、Darío Lata、Teresa Pereira、Margarita López-Torres、José M. Vila

  DOI：10.1002/zaac.200700244

  日期：2007.9

  Treatment of thiosemicarbazones (OC4H3)C(Me)=NN(H)C(=S)NHR (R: Me, a; Et, b) with [cis-PtMe2(cod)] afforded the tetranuclear compounds [Pt(OC4H2)C(Me)=NN=C(S)NHR}]4 (R: Me, 1a; Et, 1b). The reaction of 1a and 1b with triphenylphosphine in 1:4 molar ratio gave rise to the mononuclear compounds [Pt(OC4H2)C(Me)=NN=C(S)NHR}(PPh3)] (2a, 2b). Treatment of 1a and 1b with large-bite diphosphines Ph2P(CH2)nPPh2

  用 [cis-PtMe2(cod)] 处理缩氨基硫脲 (OC4H3)C(Me)=NN(H)C(=S)NHR（R：Me，a；Et，b）得到四核化合物 [Pt(OC4H2) )C(Me)=NN=C(S)NHR}]4（R：Me，1a；Et，1b）。1a 和 1b 与三苯基膦以 1:4 的摩尔比反应生成单核化合物 [Pt(OC4H2)C(Me)=NN=C(S)NHR}(PPh3)] (2a, 2b)。用大咬合二膦 Ph2P(CH2)nPPh2 (n = 2, dppe; n = 3, dppp; n = 4, dppb) 处理 1a 和 1b 得到双核化合物 -[Pt[(OC4H2)C(Me)] =NN=C(S)NHR]}2μ-Ph2P( )nPPh2}], (3a–5a, 3b–5b)，双膦处于桥接模式。与短咬合二膦 Ph2PCH2PPh2 (dppm) 和 Ph2PC(= )PPh2
• Synthesis and reactivity of dinuclear iron–platinum, chromium–platinum, molybdenum–platinum and tungsten–platinum complexes with bridging carbonyl, isocyanide and aminocarbyne ligands. An empirical study on the parameters decisive for the bonding mode of the isocyanide ligand
  作者：Michael Knorr、Isabelle Jourdain、Dieter Lentz、Stefan Willemsen、Carsten Strohmann

  DOI：10.1016/s0022-328x(03)00752-6

  日期：2003.11

  isocyanide ligand in a bridging bonding mode. Upon protonation of 2 and 3b with HBF4, the stable μ-aminocarbyne complexes [(OC)4M(μ-CN(H)R′)(μ-dppm)Pt(PPh3)][BF4] (10–11) are formed by electrophilic addition of H+ on the basic isonitrile nitrogen atom. The molecular structures of 1a,c, 2 and 3c have been determined by X-ray diffraction methods. The μ-CO and the μ-CNR ligands bridge the metal centres in an

  dppm桥接的异双金属μ-羰基配合物[（OC）4 M（μ-CO）（μ-dppm）PT（PPh 3）]（1a，M = Cr; 1b，M = Mo; 1c，M = W）已经制备由[M（CO）的反应5（η 1 -dppm）]（M =铬，钼，W）与[PT（CH 2 CH 2）（PPH 3）2 ]。化学计量的异氰酸酯加到1的结果是由CNR的π接受电子控制的。带有强吸电子取代基R的异氰酸酯配体的加成提供了异腈桥联的配合物[（OC）4 M（μ-CN–R）（μ-dppm）PT（PPh 3）] 2（M = W; R = CF 3），3（3a，M = Cr; 3b M = Mo，3c M = W; R = CH 2 SO 2 p-甲苯基）和4（M = W; R = [CH 2 PPh 3 ] [PF 6 ]。较少的π-接受异氰酸酯（R = CH 2 Ph，C 6 H 11，CH 2 PO（OEt）2），不稳
• Studies of a Reluctant Ligand. An X-ray Crystallographic and NMR Spectroscopic Analysis of (OC)₅W(η¹-PPh₂CH₂PPh₂) and Its (OC)₅W(μ-PPh₂CH₂PPh₂)W(CO)₅ Derivative
  作者：John William Benson、Richard L. Keiter、Ellen A. Keiter、Arnold L. Rheingold、Glenn P. A. Yap、Vera V. Mainz

  DOI：10.1021/om980288p

  日期：1998.9.1

  Tungsten pentacarbonyl complexes, (OC)5W(η1-PPh2CH2PPh2) (1) and (OC)5W(μ-PPh2CH2PPh2)W(CO)5 (2), have been synthesized from (OC)5WNH2Ph and Ph2PCH2PPh2 in toluene, and their solid-state structures have been determined by single-crystal X-ray diffraction. The lone pair of electrons on the dangling phosphine in 1 is oriented toward the W(CO)5 unit in the solid state, and 13C1H} and 31P1H} NMR data

  五羰基钨络合物，（OC）5 W（η 1 -PPh 2 CH 2 PPH 2）（1）和（OC）5 W（μ-PPH 2 CH 2 PPH 2）W（CO）5（2），得到了由（OC）5 WNH 2 Ph和Ph 2 PCH 2 PPh 2在甲苯中合成，并且它们的固态结构已经通过单晶X射线衍射确定。1中悬挂的膦上的孤对电子朝向W（CO）5取向单元在固态，和13 C 1 1个H}和31 p 1个H} NMR数据表明，该构象也可以在溶液中占优势。1（2 J PP = 106 Hz）中的磷-磷偶联显着大于任何以前报道的Ph 2 PCH 2 PPh 2络合物，并且高度依赖于温度和溶剂的变化。还观察到在悬空的膦与赤道碳1的羰基碳之间存在空前的长程磷碳偶合（4 J PC = 3.0 Hz），这归因于构象和/或“直通空间”的增强。根据结构和光谱数据，根据所需的大量配体构象变化，解释了1不愿意与（OC）5 WNH