trans-Fe(CO)3(PPh2H)2 | 18399-67-2

• 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: trans-Fe(CO)3(PPh2H)2
• 英文别名: carbon monoxide;diphenylphosphane;iron
• CAS: 18399-67-2；40697-11-8
• 化学式: C₂₇H₂₂FeO₃P₂
• 分子量: 512.264
• InChiKey: YZHHEKXUZFZLEO-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：

  rutheniumdichloridetricarbonyl 、 trans-Fe(CO)3(PPh2H)2 在 n-butyllithium 作用下， 以 四氢呋喃 为溶剂， 以42%的产率得到{(CO)3Ru(μ-(PPh2)2)2Fe(CO)3}*0.5CH2Cl2
  参考文献：
  名称：

  Synthesis and evaluation of the catalytic properties of homo- and hetero-bimetallic complexes containing bridging diphenylphosphido ligands

  摘要：

  The bimetallic complex [(CO)3Ru(mu-PPh2)2Ru(CO)3] (1) has been prepared in 42% yield by the reaction of [Ru3(CO)12] with tetraphenyldiphosphine in refluxing THF. Other new heterobimetallic complexes containing bridging diphenylphosphido ligands, e.g., [(CO)3Ru(mu-PPh2)2Fe(CO)3] (2), [(CO)3Ru(mu-PPh2)2M(CO)4](4: M = Cr; 5: M = Mo; 6: M = W) and [(PPh3)M'(mu-PPh2)2M(CO)4](7: M' = Pd, M = Cr; 8: M' = Pd, M = Mo; 10: M' = Pt, M = Mo) have been synthesized by the "bridge-assisted" synthetic method. The X-ray structure of [(PPh3)Pd(mu-PPh2)2 Mo(CO)4] (8) is reported. These complexes, along with [(CO)3Fe(mu-PPh2)2Fe(CO)3], [(PPh3)Pd(mu-PPh2)2W(CO)4], and [(PPh3)Pt(mu-PPh2)2W(CO)4] have been screened as catalyst precursors for (i) the hydroformylation of styrene (120-degrees-C, 20 bar, CO/H-2 = 1), and (ii) the hydrogenation of cyclohexanone (140-degrees-C, 40 bar H-2). The most efficient precursor for the first catalytic reaction was found to be the RuFe complex 2: a synergistic effect between iron and ruthenium has been observed, the turn-over frequency (TOF) increasing from 0.4 h-1 for the RuRu complex 1 and 0.9 h-1 for the FeFe complex 3, to 4.0 h-1 for the FeRu compound 2. The three complexes were recovered at the end of the catalytic reaction. In the catalytic hydrogenation of cyclohexanone, the most active was found to be the RuMo complex 5 but it was not recovered at the end of the reaction.

  DOI：

  10.1016/0022-328x(92)83047-l
• 作为产物：
  描述：

  二苯基氯化膦 在 KOH 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 生成 carbon monoxide;diphenylphosphane;iron 、 trans-Fe(CO)3(PPh2H)2
  参考文献：
  名称：

  酰基膦四羰基铁配合物的合成与反应性

  摘要：

  描述了一种由酰基柠檬酸锂和PhXPCl合成（CO）4 Fe [PPhX（C（O）R）]配合物的一般方法（R =烷基，苯基，X = Ph，Cl）。已经确定了（CO）4 Fe [PPh 2（C（O）Me）]的X射线晶体结构，并将其与其他所有具有长P–C（O）键的单核酰基膦配合物进行了比较。该键的弱点在亲核和碱性介质中有所揭示，其中（CO）4 Fe [PPh 2（C（O）R）]主要导致[（CO）4 FePPh 2 ] -阴离子。但是，在存在LDA的情况下，R = Me，n -Bu和随后添加的Ph 2会发生一些去质子化PC1以中等产率产生单齿α-次膦氧基乙烯基膦羰基铁络合物。

  DOI：

  10.1016/s0022-328x(98)01223-6

文献信息

• Ligand-variation studies on the Mössbauer effect in low-valency iron organometallic complexes: the LFe(CO)₄and L₂Fe(CO)₃series
  作者：William E. Carroll、Francis A. Deeney、John A. Delaney、Fergus J. Lalor

  DOI：10.1039/dt9730000718

  日期：——

  Room-temperature Mössbauer parameters have been measured for seven LFe(CO)4 compounds and fifteen complexes of the type L2Fe(CO)3 where L is an organophosphine or similar ligand. The trend in isomer shift values has been interpreted in terms of a dominant σ-interaction synergistically buttressed by π-bonding. A quasi-linear correlation (R= 0·92) has been found between δ and |ΔEq|.

  室温下的Mössbauer参数已针对7种LFe（CO）4化合物和15种L 2 Fe（CO）3型配合物进行了测量，其中L是有机膦或类似的配体。异构体位移值的趋势已通过由π键协同支撑的主导σ相互作用进行了解释。在δ和| ΔE q |之间发现了准线性关系（R = 0·92）。
• Synthesis and structural characterization of a phosphido-bridged heterobimetallic transition metal complex, (CO)3Fe(μ-PPh2)2Mo(CO)4
  作者：Song-Lin Li、Zheng-Zhi Zhang、Jerry C.C. Chan、Steve C.F. Au-Yeung、Thomas C.W. Mak

  DOI：10.1016/0022-328x(96)06255-9

  日期：1996.9

  heterobimetallic transition metal complex (CO)3Fe(μ-PPh2)2Mo(CO)4 (2) has been synthesized by the direct reaction of trans-(CO)3Fe(Ph2PH)2 (1) with Mo(CO)6 in benzene, and fully characterized by single-crystal X-ray analysis. Complex 2 crystallizes in the space group C2 (No. 5) with . The structure has been refined to RF = 0.032 and RwF = 0.041 for 2579 Mo K α reflections with F > 4σ(F). The two metal carbonyl

  甲异核过渡金属配合物（CO）3的Fe（μ-PPH 2）2的Mo（CO）4（2）已通过的直接反应，合成反式- （CO）3的Fe（PH 2 PH）2（1）与苯中的Mo（CO）6，并通过单晶X射线分析充分表征。配合物2在C 2（第5号）空间群中结晶。对于F > 4的2579 Mo Kα反射，结构已细化为R F = 0.032和R wF = 0.041σ（F）。两个金属羰片段通过一对μ-PPH的桥接2配体。尽管2中2.854（1）Å的FeMo距离比Fe和Mo原子的金属半径之和[ 2.66Å]长得多，但已经推断出Fe和Mo原子之间存在金属-金属键来自光谱和结构数据。
• Reactions of metal carbonyls with diphenylphosphine
  作者：J. G. Smith、D. T. Thompson

  DOI：10.1039/j19670001694

  日期：——

  equivalent of the phosphine. Di- and tri-substituted derivatives of molybdenum hexacarbonyl can be prepared by replacing unsaturated hydrocarbon ligands by the phosphine. Fe2(CO)9 reacts with PPh2H to give Fe(CO)3(PPh2H)2. Infrared and 1H and 31P nuclear magnetic resonance spectra of the diphenylphosphine products permit structural assignments. A new type of sym–asym isomerism for disubstituted octahedral

  金属羰基的单取代二苯基膦衍生物可通过将羰基与一当量的膦加热来方便地获得。可以通过用膦代替不饱和烃配体来制备六羰基钼的二取代和三取代的衍生物。Fe 2（CO）9与PPh 2 H反应，得到Fe（CO）3（PPh 2 H）2。二苯基膦产物的红外光谱和1 H和31 P核磁共振谱允许进行结构分配。一种新型的符号- ASYM用于取代八面体膦络合物推测异构。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Fe: Org.Verb.B1, 1.1.4.4.3.1, page 148 - 168
  作者：

  DOI：——

  日期：——
• Targos, Tom S.; Rosen, Richard P.; Whittle, Robert R., Inorganic Chemistry, 1985, vol. 24, # 9, p. 1375 - 1379
  作者：Targos, Tom S.、Rosen, Richard P.、Whittle, Robert R.、Geoffroy, Gregory L.

  DOI：——

  日期：——