(ferrocenylmethyl)bis(hydroxymethyl)phosphine | 180794-51-8

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: (ferrocenylmethyl)bis(hydroxymethyl)phosphine
• 英文别名: bis(hydroxymethyl)ferrocenylmethylphosphine；ferrocenylmethylbis(hydroxymethyl)phosphine；FcCH₂P(CH₂OH)₂；(η(5)-C5H5)Fe(η(5)-C5H4)CH2P(CH2OH)2；[P(CH2(η4-C5H4)Fe(η5-C5H5))(CH2OH)2]；[(η5-C5H5)Fe(η5-C5H4CH2P(CH2OH)2)]；cyclopenta-1,3-diene;[cyclopenta-2,4-dien-1-ylmethyl(hydroxymethyl)phosphanyl]methanol;iron(2+)
• CAS: 180794-51-8
• 化学式: C₁₃H₁₇FeO₂P
• 分子量: 292.098
• InChiKey: YHWMESIIJQKXFG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (ferrocenylmethyl)bis(hydroxymethyl)phosphine 在 sodium metabisulfite 作用下， 以 水 为溶剂， 生成 (ferrocenylmethyl)hydroxymethylphosphine
  参考文献：
  名称：

  An air-stable, primary alkylphosphine: FcCH2PH2 [Fc = (η5-C5H5)Fe(η5-C 5H4)]

  摘要：

  焦亚硫酸钠介导的甲醛消除 二茂铁衍生的羟甲基膦 光纤通道 2 P(CH 2 哦） 2 产生初级 膦FcCH 2 PH值 2 ，已经完全 表征，包括 X 射线晶体结构；磷化氢是 完全空气稳定。

  DOI：

  10.1039/a606580e
• 作为产物：
  描述：

  N,N,N-(ferrocenylmethyl)trimethylammonium iodide 、 三(羟基甲基)磷化氢 生成 (ferrocenylmethyl)bis(hydroxymethyl)phosphine
  参考文献：
  名称：

  Extending the range of stabilised, primary and secondary phosphanes containing ferrocenyl or ruthenocenyl groups

  摘要：

  Alkylation reactions of FcCH(2)P(CH2OH)(2) [ Fc = (eta(5)-C5H5)Fe(eta(5)-C5H4)] with MeI or p-BrCH2C6H4NO2, or of CyP(CH2OH)(2) with [FcCH(2)NMe(3)(+)]I gave hydroxymethylphosphanes FcCH(2)PR(CH2OH) (R = Me, Cy or p-O-2-NCH2C6H4) which were converted to the new secondary phosphanes FcCH(2)PHR on treatment with Na-2-S2O5. A series of longer-chain ferrocenylalkyl primary phosphanes Fc(CH2)(n)PH2 was also prepared by reactions of the bromoalkylferrocenes Fc(CH2)(n)Br (n = 4, 6 or 11) with P(CH2OH)(3) to give intermediate hydroxymethylphosphanes Fc(CH2)(n)P(CH2OH)(2), followed by reaction with Na2S2O5. Fc(CH2)(6)PH2 was converted into its crystalline BH3 adduct, which was structurally characterised. The synthesis of the new ruthenocene (Rc)-derived primary phosphane RcCH(2)PH(2), the first example of a ruthenocene-derived primary phosphane, is also reported. (C) 2014 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.ica.2014.01.049

文献信息

• Synthesis and reactivity of the ferrocene-derived phosphine [Fe(η-C5H5){η-C5H4CH2P(CH2OH)2}]
  作者：Nicholas J. Goodwin、William Henderson、Brian K. Nicholson、J. Kwabena Sarfo、John Fawcett、David R. Russell

  DOI：10.1039/a703666c

  日期：——

  The air-stable compound [Fe(η-C5H5)η-C5H4CH2P(CH2OH)2}] 1 has been prepared by the reaction of [Fe(η-C5H5)(η-C5H4CH2NMe3)]I with an excess of P(CH2OH)3. Compound 1 has been used to produce a range of other new compounds, thus demonstrating its versatility as a starting material; the phosphine oxide [Fe(η-C5H5)η-C5H4CH2P(O)(CH2OH)2}] 2, phosphine sulfide [Fe(η-C5H5)η-C5H4CH2P(S)(CH2OH)2}] 3, and other derivatives [Fe(η-C5H5)η-C5H4CH2P(CH2CH2CN)2}] 4, [Fe(η-C5H5)η-C5H4CH2P(CH2NEt2)2}] 5, [Fe(η-C5H5)η-C5H4CH2P(O)(CH2NEt2)2}] 6, [Fe(η-C5H5)η-C5H4CH2P(Me)(CH2OH)2}]I 7 and [Fe(η-C5H5)η-C5H4CH2P(Me)CH2OH}] 8. Crystal structure determinations for 1, 3 and 7 are reported and the hydrogen bonding of each structure described.

  空气稳定化合物 [Fe(η-C5H5)η-C5H4CH2P(CH2OH)2}] 1 通过 [Fe(η- )(η-C5H4CH2NMe3)]I 与过量 P(CH2OH)3 反应制备。化合物 1 已被用于合成一系列其他新化合物，从而展示了其作为起始材料的多样性；包括膦氧化物 [Fe(η- )η-C5H4CH2P(O)(CH2OH)2}] 2，膦硫化物 [Fe(η- )η-C5H4CH2P(S)(CH2OH)2}] 3，以及其他衍生物 [Fe(η- )η-C5H4CH2P(CH2CH2CN)2}] 4，[Fe(η- )η-C5H4CH2P(CH2NEt2)2}] 5，[Fe(η- )η-C5H4CH2P(O)(CH2NEt2)2}] 6，[Fe(η- )η-C5H4CH2P(Me)(CH2OH)2}]I 7 和 [Fe(η- )η-C5H4CH2P(Me)CH2OH}] 8。报道了 1、3 和 7 的晶体结构测定，并描述了每种结构的氢键。
• Unexpected Synthesis of Tetrahedral Fe/S Clusters via Highly Reactive Butterfly Intermediates (μ-HS)₂Fe₂(CO)₅[RP(CH₂OH)₂]
  作者：Li-Cheng Song、Pei-Hua Zhao、Zong-Qiang Du、Ming-Yi Tang、Qing-Mei Hu

  DOI：10.1021/om100793d

  日期：2010.11.22

  (μ-HS)2Fe2(CO)6 (1) with RP(CH2OH)2 under N2 followed by TLC separation in air gave the unexpected tetrahedral complexes (μ-S2)Fe2(CO)5[RP(CH2OH)2] (4a, R = Ph; 4b, η5-C5H4CH2FeCp). While the suggested pathway for production of 4a,b was proved by isolation and characterization of the very air-sensitive intermediate (μ-HS)2Fe2(CO)5[PhP(CH2OH)2] (M1), the in situ reaction of M1 with I(CH2)3I and Et3N allowed

  蝴蝶的反应复合物（μ-HS）2的Fe 2（CO）6（1用RP（CH）2 OH）2氮气氛下2然后在空气中TLC分离，得到意想不到的四面体配合物（μ-S 2）的Fe 2（ CO）5 [RP（CH 2 OH）2 ]（图4a，R = Ph值;图4b，η 5 -C 5 H ^ 4 CH 2 FeCp）。虽然建议的生产4a，b的途径通过对空气非常敏感的中间体（μ-HS）2 Fe 2（CO）5 [PhP（CH 2 OH）2 ]（M 1）的分离和表征，M 1与I（CH ）的原位反应来证明2）3 I和Et 3 N使我们能够获得模型复合物（μ-PDT）Fe 2（CO）5 [PhP（CH 2 OH）2 ]（5）。
• Synthesis and structure of ferrocenylmethylphosphines, their borane adducts, and some related derivatives
  作者：Mitchell A. Pet、Matthew F. Cain、Russell P. Hughes、David S. Glueck、James A. Golen、Arnold L. Rheingold

  DOI：10.1016/j.jorganchem.2009.03.015

  日期：2009.6

  treatment of 1 with Me3SiCl/Et3N gave FcCH2P(CH2OSiMe3)2 (11). The phosphine-borane adducts FcCH2PH2(BH3) (6), (FcCH2)2PH(BH3) (7), (FcCH2)3P(BH3) (8) and (FcCH2)P(CH2OSiMe3)2(BH3) (15) were prepared from the corresponding phosphines and BH3(SMe2). The phosphines 2, 3, and 4, phosphonium salts 5 and 13, phosphine oxide 12, Pt complex trans-14, and phosphine-boranes 6, 7 and 8 were structurally characterized

  已知ferrocenylmethylphosphines的合成FCCH 2 PH 2（2，FC =（η 5 -C 5 H ^ 4）的Fe（η 5 -C 5 H ^ 5）），（FCCH 2）2 PH（3），和（FCCH 2）3 P（4）已重新研究。的反应〔FCCH 2 NME 3 ] [I]与P（CH 2 OH）3，从生成的[P（CH 2 OH）4 ] [CL]和KOH，得到主要产物的混合物（FCCH 2）P（CH 2 OH）2（1）和高烷基化（FcCH 2）2 P（CH 2 OH）（9）。用Na 2 S 2 O 5处理纯9得到仲膦3 ; 将Na 2 S 2 O 5缓慢加入到1中，产率提高了2。的反应1与[FCCH 2 NME 3 ] [I]中，接着用净处理3，得到叔膦（FCCH 2）3 P（4）以及已知的phospho盐[（FcCH 2）4 P] [I]（5），可以通过调节化学计量比以更高
• Tetraacetatodirhodium(II) complexes with tris(methoxyphenyl)phosphines, their reactivity, structure, and antitumor activity
  作者：Florian P Pruchnik、Radoslaw Starosta、Zbigniew Ciunik、Adam Opolski、Joanna Wietrzyk、Elzbieta Wojdat、Danuta Dus

  DOI：10.1139/v01-080

  日期：2001.5.1

  Reactions of [Rh₂(µ-OAc)₄(H₂O)₂] ([1·(H₂O)₂]) with tris(3-methoxyphenyl)phosphine at 1:1 and 1:2 molar ratios yield, first, the appropriate adducts: [1·(H₂O)P(C₆H₄-3-OMe)₃}] and [1·P(C₆H₄-3-OMe)₃}₂], and then [Rh₂(µ-OAc)₃µ-(C₆H₃-3-OMe)P(C₆H₄-3-OMe)₂}(HOAc)₂] ([2·(HOAc)₂]), and [Rh₂(µ-OAc)₂µ-(C₆H₃-3-OMe)P(C₆H₄-3-OMe)₂}₂(HOAc)₂] ([3·(HOAc)₂]) complexes, respectively. They have been characterized by spectroscopic methods. The molecular structure of [3·(HOAc)(H₂O)] has been determined crystallographically. The complexes [3·(HOAc)₂], [Rh₂(µ-OAc)₃µ-(C₆H₃-4-OMe)P(C₆H₄-4-OMe)₂}(HOAc)₂] ([4·(HOAc)₂]), and [Rh₂(µ-OAc)₂µ-(C₆H₃-4-OMe)P(C₆H₄-4-OMe)₂}₂(HOAc)₂] ([5·(HOAc)₂]) reversibly react with CO giving mono- and biadducts. Antitumor activity of binuclear rhodium(II) compounds [3·(HOAc)₂], [Rh₂(µ-OAc)₃µ-(C₆H₃-2-O)P(C₆H₃-2-OMe)₂}(HOAc)] ([6·(HOAc)]), and [Rh₂(µ-OAc)₃µ-(C₆H₃-6-OMe-2-O)P[(C₆H₃-2,6-(OMe)₂]₂}(HOAc)] ([7·(HOAc)]) have been investigated in vitro. The most active agent for investigated tumor lines is complex [6·(HOAc)]. It shows higher activity than cisplatin (cis-[PtCl₂(NH₃)₂]). Antitumor activity decreases in the series: [6·(HOAc)] > [7·(HOAc)] > [3·(HOAc)₂]. Activity of all investigated rhodium(II) complexes is higher than that of [1·(H₂O)₂].Key words: dirhodium(II) complexes, functionalized phosphines, aryl phosphines, ferrocenylmethylphosphines, adducts with CO, antitumor activity, orthometallation reactions.

  [1·(H₂O)₂]与三(3-甲氧基苯基)膦以1:1和1:2的摩尔比反应，首先生成相应的加合物：[1·(H₂O)P(C₆H₄-3-OMe)₃}]和[1·P(C₆H₄-3-OMe)₃}₂]，然后分别生成[Rh₂(µ-OAc)₃µ-(C₆H₃-3-OMe)P(C₆H₄-3-OMe)₂}(HOAc)₂] ([2·(HOAc)₂])和[Rh₂(µ-OAc)₂µ-(C₆H₃-3-OMe)P(C₆H₄-3-OMe)₂}₂(HOAc)₂] ([3·(HOAc)₂])配合物。它们通过光谱方法进行了表征。[3·(HOAc)(H₂O)]的分子结构已通过晶体学确定。配合物[3·(HOAc)₂],[Rh₂(µ-OAc)₃µ-(C₆H₃-4-OMe)P(C₆H₄-4-OMe)₂}(HOAc)₂] ([4·(HOAc)₂])和[Rh₂(µ-OAc)₂µ-(C₆H₃-4-OMe)P(C₆H₄-4-OMe)₂}₂(HOAc)₂] ([5·(HOAc)₂])可逆地与CO反应，形成单加合物和双加合物。[3·(HOAc)₂],[Rh₂(µ-OAc)₃µ-(C₆H₃-2-O)P(C₆H₃-2-OMe)₂}(HOAc)] ([6·(HOAc)])和[Rh₂(µ-OAc)₃µ-(C₆H₃-6-OMe-2-O)P[(C₆H₃-2,6-(OMe)₂]₂}(HOAc)] ([7·(HOAc)])的二核铑(II)化合物的体外抗肿瘤活性已经被研究。对于所研究的肿瘤细胞系，最活跃的药物是[6·(HOAc)]。它的活性比顺铂(cis-[PtCl₂(NH₃)₂])更高。所有研究的铑(II)配合物的抗肿瘤活性均高于[1·(H₂O)₂]。关键词：二核铑(II)配合物，功能化膦，芳基膦，二茂铁甲基膦，与CO的加合物，抗肿瘤活性，正金属化反应。
• Electrochemistry of ferrocenylphosphines FcCH2PR2 (Fc=(η5-C5H5)Fe(η5-C5H4); R=Ph, CH2OH and CH2CH2CN), and some phosphine oxide, phosphine sulfide, phosphonium and metal complex derivatives
  作者：Alison J. Downard、Nicholas J. Goodwin、William Henderson

  DOI：10.1016/s0022-328x(03)00309-7

  日期：2003.6

  (Fc=(η5-C5H5)Fe(η5-C5H4); R=Ph, CH2OH and CH2CH2CN) and some phosphine oxide, phosphine sulfide, phosphonium and metal derivatives are described. The free ligands exhibit complex voltammetric responses due to participation of the phosphorus lone pair in the redox reactions. Uncomplicated ferrocene-based redox chemistry is observed for PV derivatives and when the ligands are coordinated in complexes ci

  自由二茂铁的电化学研究配体FCCH 2 PR 2（FC =（η 5 -C 5 H ^ 5）的Fe（η 5 -C 5 H ^ 4）; R =苯基，CH 2 OH和CH 2 CH 2 CN）和一些描述了氧化膦，硫化膦，phospho和金属衍生物。游离配体由于磷孤对参与氧化还原反应而表现出复杂的伏安响应。观察到P V衍生物以及配体在顺式-PtCl 2络合物中配位时，不复杂的基于二茂铁的氧化还原化学反应[FCCH 2 P（CH 2 OH）2 ]，的PdCl 2 [FCCH 2 P（CH 2 OH）2 ]，[金FCCH 2 P（CH 2 OH）2 } 2 ]氯，的RuCl 2（η 6 -C 10 ħ 14）[FCCH 2 P（CH 2 OH）2 ]和的RuCl 2（η 6 -C 10 ħ 14）（FCCH 2 PPH 2）。使用伏安法，NMR光谱法和电喷雾质谱法已经详细研究了单电子氧化后游离配体的