pentacarbonyl(trimethylphosphite)chromium(0) | 18461-34-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 亚磷酸三烷基酯
• 英文名称: pentacarbonyl(trimethylphosphite)chromium(0)
• 英文别名: Carbon monoxide;chromium;trimethyl phosphite；carbon monoxide;chromium;trimethyl phosphite
• CAS: 18461-34-2
• 化学式: C₈H₉CrO₈P
• 分子量: 316.124
• InChiKey: OXGMWGFHFYVFCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,4-二甲基-1,3-戊二烯 、 pentacarbonyl(trimethylphosphite)chromium(0) 以 正戊烷 为溶剂， 以36%的产率得到
  参考文献：
  名称：

  Michael, Guenther; Kaub, Juergen; Kreiter, Cornelius G., Angewandte Chemie, 1985, vol. 97, p. 503 - 505

  摘要：

  DOI：
• 作为产物：
  描述：

  以 neat (no solvent) 、 further solvent(s) 为溶剂， 生成 pentacarbonyl(trimethylphosphite)chromium(0)
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: Org.Verb., 1.1.2.1.4.2, page 54 - 62

  摘要：

  DOI：
• 作为试剂：
  描述：

  三乙基硅烷 、 1,3-丁二烯 在 pentacarbonyl(trimethylphosphite)chromium(0) 作用下， 以 正己烷 为溶剂， 生成 (Z)-but-2-en-1-yltriethylsilane
  参考文献：
  名称：

  Photocatalytic hydrosilylation of conjugated dienes with triethylsilane in the presence of Cr(CO)5L (L = CO, P(CH3)3, P(OCH3)3)

  摘要：

  The effect of donor ligands on the chromium carbonyl photocatalysed hydrosilylation of 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, trans-1,3-pentadiene with triethylsilane was studied. Photocatalytic hydrosilylation of dienes conducted in the presence of Cr(CO)(5)L (L = P(CH3)(3) or P(OCH3)(3)) yields the cis-1,4-adducts, 1-triethylsilyl-2-butene derivatives, as the main products; these have been isolated by distillation or preparative GC and fully characterised by NMR spectroscopy. As with the photocatalytic hydrosilylation of dienes in the presence of Cr(CO)(6), we propose a mechanism which involves the initial conversion of Cr(CO)(5)L into fac-Cr(CO)(3)L(eta(4)-1,3-diene) followed by a further photolytic CO substitution by triethylsilane, forming a Cr(CO)(2)(H)(SiEt3)L(eta(4)-1,3-diene)intermediate. The addition of hydride to diene occurs reversibly to form an eta(3)-enyl ligand prior to the irreversible silyl transfer to the organic moiety. The 1,4-hydrosilylation adduct is then replaced by new substrates to complete the catalytic cycle. Cr(CO)SL complexes form active species which are much more stable than the one generated from CI(CO), in the absence of any donor ligands. Thus, introduction of an equimolar amount of donor ligand (trimethylphosphine or trimethylphosphite) increases the Life of the catalyst. This leads to the achievement of larger turn-over numbers (80 or 70) compared with the value of 30 for just Cr(CO)(6). Cr(CO)(5)L (L = P(C6H5)(3), P(C6H11)(3) or C5H5N) proved inactive in the attempted photocatalytic hydrosilylation of dienes.

  DOI：

  10.1016/s0022-328x(96)06843-x

文献信息

• Sonochemistry and sonocatalysis of metal carbonyls
  作者：Kenneth S. Suslick、James W. Goodale、Paul F. Schubert、Hau H. Wang

  DOI：10.1021/ja00356a014

  日期：1983.9

  67 The labeled precursor utilized in the present investigation, 1-deoxy-D-three [ l-2H3,5-2Hl]pentulose (6) was synthesized from 2,4-O-benzylidene-~-[4-~H~] threose, which is available from D[ l-2Hl]arabinitol by standard Reaction of the threose derivative with trideuteriomethylmagnesium iodide in ether then gave a mixture of protected, epimeric pentane tetrols, which was oxidized by the stannylene

  然后提取硫胺素，并用亚硫酸氢盐裂解，以通常的方式得到 HET。将其转化为三氟乙酸酯用于 MS 检查。
• Gehinderte Ligandbewegungen in übergangsmetallkomplexen
  作者：Cornelius G. Kreiter、Michael Kotzian、Saim Özkar、Izzet Abu-Mour

  DOI：10.1016/0022-328x(92)80115-e

  日期：1992.6

  5-diene-trimethylphosphite-metal(0) and cis-dicarbonyl-η4-tricyclo[6.3.0.0 2,7]undeca-3,5-diene-bis(trimethylphosphite)metal(0) complexes of chromium (1, 4), molybdenum (2, 5) and tungsten (3, 6) have been prepared photochemically in high yields from the corresponding pentacarbonyl-trimethylphosphite-metal(0) or tetracarbonyl-bis (trimethylphosphite) metal(0) complexes, respectively, with tricyclo[6

  三羰基-η 4 -三环[6.3.0.0 2,7 ]十一碳-3,5-二烯亚磷酸三甲酯-金属（0）和顺式二羰基-η 4 -三环[6.3.0.0 2,7 ]十一碳-3,5- -二烯-双（亚磷酸三甲酯）金属（0）铬（配合物1，4），钼（2，5）和钨（3，6）已在从相应的五羰基-亚磷酸三甲酯，金属高的产率制备的光化学（0 ）或四羰基双（亚磷酸三甲酯）金属（0）配合物，分别与三环[6.3.0.0 2,7 ] undeca -3,5-diene。的立体化学1 -通过IR和NMR光谱确定图6。在三羰基-η的情况下，4 -三环[6.3.0.0 2,7 ]十一碳-3,5-二烯亚磷酸三甲酯-钨（0）（3），X射线晶体和分子结构分析确认的结论从拉光谱数据。失真伪八面体配合物1 - 3专门得到˚F -异构体，和4 - 6作为AF -异构体。根据它们与温度有关的NMR光谱，它们都显示出受阻的配体运动。对于1 – 3羰基加扰，对于4
• Kinetic studies of the cleavage of M+[M′M″(CO)9L]− (M+  Na+, PPN+; M′  Cr, W; M″  Mn, Re; L  CO, PR3)
  作者：Yong K. Park、Seon J. Kim、Jin H. Kim、In S. Han、Chang H. Lee、Hyung S. Choi

  DOI：10.1016/0022-328x(91)86383-2

  日期：1991.5

  heterobimetallic species of interest, M+[M′M″(CO)9L]− (M+ = Na+; M′  Cr, W; M″  Mn, Re; L  CO, PR3) undergoes ligand substitution or metal-metal bond cleavage upon reaction with PR3 (R  C6H5, C2H5) or CO. Unprecedented reactions by the counter ion were observed. Factors affecting these dimeric disruptions will be discussed on the basis of the kinetic studies.

  异双金属配合物具有供体-受体金属-金属键，其中来自富电子金属部分的两个电子被提供给另一个缺电子的金属部分。感兴趣的杂双金属物质M + [M'M''（CO）9 L] -（M + = Na +； M'Cr，W; M“Mn，Re; LCO，PR 3）经历配体在与PR反应取代或金属-金属键断裂3（Rç 6 ħ 5，C 2 H ^ 5）或CO。由抗衡离子前所未有的反应中观察到。将在动力学研究的基础上讨论影响这些二聚体破坏的因素。
• Metal-to-ligand charge-transfer excited-state photochemistry of [Cr(CO)₅(C₄H₄N₂)] and [Cr(CO)₄(NC₅H₄CHNPrⁱ)]. The difference between the photochemical behaviour of [Cr(CO)₅(C₄H₄N₂)] in solution at 243 K and in an argon matrix at 10 K
  作者：Roelof W. Balk、Gosse Boxhoorn、Theo L. Snoeck、Gerard C. Schoemaker、Derk. J. Stufkens、Ad Oskam

  DOI：10.1039/dt9810001524

  日期：——

  Irradiation of [Cr(CO)4(NC5H4CHNPri)] in solution within the lowest Cr-to-di-imine charge-transfer band causes photosubstitution of a cis carbonyl ligand. Free CO and fac-[Cr(CO)3(NC5H4CHNPri)] are formed when the complex is irradiated within this absorption band in matrices at 10 K. On the other hand, irradiation of a solution of [Cr(CO)5(C4H4N2)] within the Cr-to-pyridazine charge-transfer band mainly

  在最低的Cr-二亚胺电荷转移带内的溶液中辐照[Cr（CO）4（NC 5 H 4 CH NPr i）]导致顺式羰基配体光解。当在该吸收带内以10 K的矩阵辐照络合物时，会生成游离的CO和fac- [Cr（CO）3（NC 5 H 4 CH NPr i）]。另一方面，辐照[Cr]溶液（CO）5（C 4 H 4 N 2）]在Cr到哒嗪的电荷转移带中，主要是引起哒嗪的光吸收，而游离的CO和顺式[[Cr（CO）4（C 4 H 4 N 2）]]形成于基质中。这些结果与金属到配体的电荷转移激发态的寿命以及这些配合物的共振拉曼光谱有关。
• Pentacarbonyl (η²-cis-cyclo-octene)chromium: photochemical synthesis of a useful Cr(CO)₅transfer reagent
  作者：Friedrich-Wilhelm Grevels、Volker Skibbe

  DOI：10.1039/c39840000681

  日期：——

  (η2-olefin)nCr(CO)6-n conplexes result from the photoreactions of Cr(CO)6 with cis-cyclo-octene (n = 1) and trans-cyclo-octene (n = 1, 2); (n = 1,2); (η2-cis-cyclo-octene)Cr(CO)5, isolated as a yellow solid, is labile in solution and serves as a useful Cr(CO)5 transfer reagent to produce various LCr(CO)5 derivatives, including the isotopically labelled hexacarbonyl, Cr(CO)5(13CO).

  （η 2烯烃）Ñ的Cr（CO）6- ñ conplexes选自Cr（CO）的光反应导致6与顺式-环辛烯（N = 1）和反式-环辛烯（N = 1，2）; （n = 1,2）；（η 2 -顺式-环辛烯）的Cr（CO）5，分离出黄色固体，是不稳定的溶液中，并作为一个有用的Cr（CO）5转移试剂以产生各种LCR（CO）5组的衍生物，其中包括同位素标记的六羰基Cr（CO）5（13 CO）。

表征谱图