cis-Me₂Fe(PMe₃)₄ | 64524-92-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机过渡后金属化合物
• 英文名称: cis-Me₂Fe(PMe₃)₄
• 英文别名: Carbanide;iron(2+);trimethylphosphane
• CAS: 64524-92-1
• 化学式: C₁₄H₄₂FeP₄
• 分子量: 390.23
• InChiKey: GDNVXMTXCIRTCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-Me₂Fe(PMe₃)₄ 、 (E)-N-烯丙基-1-苯基甲亚胺 以 四氢呋喃 为溶剂， 反应 24.0h， 以87%的产率得到
  参考文献：
  名称：

  Fe(IV) alkylidenes are actually Fe(II), and a related octahedral Fe(II) “alkylidene” is a conjugated vinyl complex

  摘要：

  Electronic structure calculations on previously synthesized [mer-(kappa-C,N,C-(2-C6H4)CH=N(1,2-C6H4) C(Pr-i)=Fe(PMe3)(3)][BAr4F] (1) and mer,trans-(kappa-C,N,C-(2-C6H4)CH(Bn)N(1,2-C6H4)C(Pr-i)=}Fe(PMe3)(2)N-2 (4-Bn) reveal that 1 is best interpreted as Fe(II) bound to a carbenium ion, while 4-Bn has an imino-vinyl unit bound to a ferrous center. Attempts to prepare LnFe=CHR species capable of olefin metathesis or carbene transfer were obviated by alternative reactivity, although precursors mer,trans-{kappa(3)-N,N,C-(2-py) CH=NCH2CH=CH}Fe(PMe3)(2)CH3 (6), [mer,trans-{kappa(3)-N,N,C-2-py-CH=NCH2CH=CH}Fe(PMe3)(2)CH3] [PF6-] (8), mer,trans-{kappa(3)-N,N,C-2-py-CH=NCH2CH=CH}Fe(PMe3)(2)I (9), mer-{kappa(3)-N,N,C-(2-pyridyl) CHNCHCHCH} Fe(PMe3)(3) (11), and mer-{kappa(3)-C,N,C-(2-C6H4)CH=NCH2CH=CH}Fe(PMe3)(3) (12) were prepared. Related phenyl derivatives, mer,trans-{kappa(3)-N,N,C-(2-py)CH=NC(Me)(2)CH=CH}Fe(PMe3)(2)CH3 (13) and [mer,trans-kappa(3)-N, N,C-(2-py)CH=NC(Me)(2)CH=CH}Fe(PMe3)(2)N-2][BAr4F] (15) were prepared to test additional stability issues. Compounds 9 and 11 were structurally characterized, and metrical parameters of the latter, in addition to electronic structure calculations, suggest that it is not an alkylidene, but an Fe(II) center coordinated by a conjugated vinyl ligand with extensive delocalization in its pi-system. (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2016.04.030

文献信息

• Fe(<scp>iv</scp>) alkylidenes via protonation of Fe(<scp>ii</scp>) vinyl chelates and a comparative Mössbauer spectroscopic study
  作者：Brian M. Lindley、Ala'aeddeen Swidan、Emil B. Lobkovsky、Peter T. Wolczanski、Mario Adelhardt、Jörg Sutter、Karsten Meyer

  DOI：10.1039/c5sc01268f

  日期：——

  Fe(iv) alkylidenes are produced via protonation of Fe(ii) vinyl chelate complexes.

  Fe(IV) 烷基烯基金属配合物是通过对Fe(II) 乙烯螯合物进行质子化得到的。
• Selective Extraction of N₂ from Air by Diarylimine Iron Complexes
  作者：Erika R. Bartholomew、Emily C. Volpe、Peter T. Wolczanski、Emil B. Lobkovsky、Thomas R. Cundari

  DOI：10.1021/ja311021u

  日期：2013.3.6

  to air or N2 (1 atm), yielding mer-κC,N,C'-(Ar-2-yl)CH2N═CH(Ar'-2-yl)}Fe(PMe3)2L (L = N2, 2a-f); CO, CNMe, and N2CPh2 derivatives (L = CO, 3a-d,f; L = CNMe, 8b; L = N2CPh2, 9b) were prepared. Dihydrogen or NH3 binding to mer-κC,N,C'-(3,4,6-(F)3-C6H-2-yl)CH2N═CH-(3,4,5-(F)3-C6H-2-yl)}Fe(PMe3)2 (1b', S = 1 (calc)) to provide 5b (L = H2) or 6b (L = NH3) was found comparable to that of N2, while PMe3

  用邻位取代的二芳基亚胺处理顺式-(Me3P)4FeMe2 得到 2 当量的 MeH、PMe3 和 mer-κC,N,C'-(Ar-2-yl)CH2N=CH(Ar'-2-yl) }Fe(PMe3)3 (Ar = 3,4,6-(F)3-C6H, Ar' = 3,5-(CF3)2-C6H2, 1a; Ar = 3,4,6-(F)3 -C6H，Ar' = 3,4,5-(F)3-C6H，1b；Ar = 4,5,6-(F)3-C6H，Ar' = 3,5-( )2- ， 1c; Ar = C6H4, Ar' = 3-(OMe)-C6H3, 1d; Ar = 4,5,6-(F)3-C6H, Ar' = 3,6-Me2- , 1e; Ar = , Ar' = 3,6-Me2- , 1f)。1a-f 暴露于 O2 导致快速降解，但当 1a-f 暴露于空气或 N2 (1 atm)
• High- and low-spin chelate complexes of iron featuring κ-C,X-CH2C6H4X (X = NMe2, PMe2, PPh2) and κ-C,P-CH2PMe2 ligands
  作者：Brian P. Jacobs、Peter T. Wolczanski、Samantha N. MacMillan

  DOI：10.1016/j.jorganchem.2017.04.001

  日期：2017.10

  Several C,X-chelate complexes of iron were generated via standard metathetical procedures. Treatment of FeCl2 and LnFeCl2 (L = Me2IPr, n = 1; PMe3, n = 2) with anionic equivalents o-LiCH2C6H4NMe2, o-LiCH2C6H4PPh2, and LiCH2PMe2 led to the preparation of [Fe(o-CH2C6H4NMe2)]2(κ-μ-CH2,N-o-CH2C6H4NMe2)2 (1, X-ray), [fac-Fe(κ-C,P-o-CH2C6H4PPh2)3][Li(TMEDA)2] (2, X-ray), (Me2IPr)Fe(CH2C6H4-o-NMe2)2 (3-C

  通过标准复分解方法生成了几种铁的C，X螯合物。用阴离子当量o-LiCH 2 C 6 H 4 NMe 2，o- LiCH 2 C 6 H 4 PPh处理FeCl 2和L n FeCl 2（L = Me 2 IPr，n = 1; PMe 3，n = 2）2，和的LiCH 2 PME 2为首的制备的[Fe（O-CH 2 C ^ 6 ħ 4 NME 2）] 2（κ-μ-CH 2，No-CH 2 C 6 H 4 NMe 2）2（1，X射线），[ fac -Fe（κ-C，Po-CH 2 C 6 H 4 PPh 2）3 ] [Li（TMEDA）2 ] （2，X射线），（Me 2 IPr）Fe（CH 2 C 6 H 4 -o-NMe 2）2（3 -C，N），[（Me 2 IPr）2 Fe]（μ-κ- C，P-CH 2 PMe 2）2 [Fe（κ-C，P-CH2 PMe 2）2 ]（4，X射线）和（PMe 3）2
• Aryl-Containing Pyridine-Imine and Azaallyl Chelates of Iron toward Strong Field Coordination Compounds
  作者：Emily C. Volpe、Peter T. Wolczanski、Emil B. Lobkovsky

  DOI：10.1021/om900793c

  日期：2010.1.25

  CH4 and py CH activation to provide mer-κ-C,N,C′-(p-tBu-Ar-2-yl)CH═NCH2(2-py-3-yl)}(PMe3)3FeII (6). Derivatization of 6 with MeOTf produced [mer-κ-C,N,C′-(p-tBu-Ar-2-yl)CH═NCH2(2-py-NCH3-3-yl)}(PMe3)3FeII]OTf (7), which could be deprotonated to give the zwitterionic azaallyl mer-κ-C,N,C′-(p-tBu-Ar-2-yl)CHNCH(2-py-NCH3-3-yl)}(PMe3)3FeII (8). Oxidation of 4 with AgOTf generated [trans-κ-C,N,N′-(p-t

  已经准备了一系列的芳基和吡啶基亚胺铁配合物，以探索由芳基螯合物提供的强场的产生以及氮杂烯丙基官能团的潜在支持。顺式-（Me 3 P）4 FeMe 2和基于亚氨基的配体前体提供了反式-κ- C，N，N '-（XAr-2-yl）CH 2 N 2CH-2a href=https://www.molaid.com/MS_309980 target="_blank">2-Py}（PMe 3）2 Fe II CH 3（X = H，1 ; p -OMe，2 ; o -Cl，3）和反式-κ-Ç，Ñ，Ñ ' - （p -吨卜氩-2-基）= NCH 2 -2-吡啶}（PME 3）2的Fe II CH 3（4）伴随2 PME 3和CH 4通过ARH激活。热解4 + PME 3给CH 4和PY CH活化，以提供聚体- κ- Ç，Ñ，Ç ' - （p -吨卜氩-2-基）= NCH 2（2-PY-3- yl）}（PMe 3）3 Fe II（6）。的衍生化6与MeOTf产生[聚体- κ- Ç，Ñ，C' - （p -吨卜氩-2-基）=
• Syntheses and characterizations of α-iminopyridine compounds (alkylNCHpy)2Fe(L/Xn), and an assessment of redox non-innocence
  作者：Emily C. Volpe、Peter T. Wolczanski、Jonathan M. Darmon、Emil B. Lobkovsky

  DOI：10.1016/j.poly.2012.08.060

  日期：2013.3

  Treatment of cis-(Me3P)(4)FeMe2 with two equiv (neo)PeN=CH(2-py) afforded kappa-N,N'-(neo)PeN=CH(2-pyridy1))(2)FeMe2 (2-P). Reductions of FeCl2 with Na/Hg in the presence of (neo)PeN=CH(2-pyridyl) or (neo)HexN=CH(2-pyridyl) and L (H2C=CHCO2Me, PhCCPh, PMe3) gave tentative evidence of [kappa-N,N'-(neo)PeN=CH(2-pyridy1)}(2)Fe(H2C=CHCO2Me) (2-P), but (x-N,N'-(neo)PeN=CH(2-pyridyI)}(2)Fe(PhCCPh) (5-P), (kappa-N,N'-neoHexN=CH(2-pyridy1)}(2)Fe(PhCCPh) (5-H), and kappa-N,N'-(neo)HexN=CH(2-pyridy1))(2-)Fe(PMe)}(2-) (6-H) were all isolated in good yield. Phosphine complex 6-H could be alkylated with CH3I or CH3OTf to afford kappa-N,N'-(neo)HexN=CH(2-pyridyl)}(2-)Fe(PMe3)Me]I-+(-) (7-H-I) or kappa-N,N'-(neo)HexN=CH(2-pyridyl)}(2-)Fe(PMe3)Me]I-+(-) OTf- (7-H-OTf) center dot [kappa-N,N'-RN=CH(2-pyridyl)}(3-)Fe][OTf](2) (R = (neo)Pe, 8-P-OTf; (neo-)Hex, 8-H-OTf) omplexes were also prepared from Fe(OTO)(2) in order to identify potential byproducts in certain reactions. Compounds 2-P and 7-H-0Tf were tested for ethylene oligomerization activity, to no avail. Complexes 2-P, 5-H, 6-H, and 7-H-OTf were structurally characterized and evaluated by Mossbauer spectroscopy, and 5-H was shown to possess a redox non-innocent alkyne ligand, while the alpha-alkyliminopyridine ligands of 6-H were classified as radical anions, rendering all compounds describable as Fe(ll). (C) 2012 Elsevier Ltd. All rights reserved.