trans-Mo(N)Cl(Ph2PCH2CH2PPh2)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-Mo(N)Cl(Ph2PCH2CH2PPh2)2
• 英文别名: [Mo(N)(Cl)(dppe)2]；Azanylidyne(chloro)molybdenum;2-diphenylphosphanylethyl(diphenyl)phosphane
• 化学式: C₅₂H₄₈ClMoNP₄
• 分子量: 942.248
• InChiKey: SGXVSFAMJYXUOW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.21
• 重原子数：
  59
• 可旋转键数：
  14
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-Mo(N)Cl(Ph2PCH2CH2PPh2)2 、 氘代盐酸 以 not given 为溶剂， 生成 [Mo(ND)(Cl)(dppe)2]Cl
  参考文献：
  名称：

  钼，亚硝酸钨和亚氨基钨配合物与二膦大分子配体的电子结构，光谱性质和反应性：反式配体的影响。

  摘要：

  一系列的钼和钨氮化物[M（N）（X）（diphos）2]和亚胺基络合物[M（NH）（X）（diphos）2）] Y，（M = Mo，W）研究了双膦大分子配体（diphos = dppe / depe），各种反式配体（X = N3-，Cl-，NCCH3）和不同的抗衡离子（Y- = Cl-，BPh4-）。通过红外和拉曼光谱研究了这些化合物。还对它们进行了同位素取代和光吸收以及发射光谱学研究。在具有反叠氮基和-氯大肠菌素的亚硝酸盐配合物中，金属N的延伸量大约为980 cm（-1）。质子化后，它降低到约920 cm（-1）。在398 nm处观察到[Mo（N）（N3）（depe）2]的1A1-> 1E（n-> pi）电子跃迁，并显示了810 cm（-1）的金属N拉伸过程）。在542 nm处观察到相应的3E-> 1A（pi-> n）发射带，在980 cm（-1）的金属N拉伸中表现出进展。在亚氨基系统[Mo（NH）（N3）（depe）2]

  DOI：

  10.1021/ic060141n
• 作为产物：
  描述：

  trans-{Mo(NH)(Cl)(Ph2PC2H4PPh2)}(1+) 以 四氢呋喃 为溶剂， 以90%的产率得到trans-Mo(N)Cl(Ph2PCH2CH2PPh2)2
  参考文献：
  名称：

  Alias, Yatimah; Ibrahim, Saad K.; Queiros, M. Arlete, Journal of the Chemical Society, Dalton Transactions

  摘要：

  DOI：

文献信息

• From metal imides and molecular nitrogen to ammonia and dinitrogen complexes
  作者：Modher Y. Mohammed、Christopher J. Pickett

  DOI：10.1039/c39880001119

  日期：——

  Reduction of a molybdenum imide under molecular nitrogen gives ammonia and a dinitrogen complex.

  在分子氮下还原钼酰亚胺得到氨和二氮配合物。
• Electrosynthesis of amino acids from a molybdenum nitride via nitrogen–carbon and carbon–carbon bond formation reactions involving imides and nitrogen ylides: X-ray structure of trans-[MoCl(NCHCO₂Me)(Ph₂PCH₂CH₂PPh₂)₂]·CH₂Cl₂
  作者：David L. Hughes、Saad K. Ibrahim、Colin J. Macdonald、Hapipah Mohd. Ali、Christopher J. Pickett

  DOI：10.1039/c39920001762

  日期：——

  Sequential nitrogen–carbon and carbon–carbon bond formation, and an electrochemical Mo–N bond cleavage step, define a pathway to methyl esters of the amino acids glycine and alanine from the molybdenum nitride trans-[MoCl(N)(Ph2PCH2CH2PPh2)2], a key intermediate being the metallo-nitrogen ylide trans-[MoCl(NCHCO2Me)(Ph2PCH2CH2PPh2)2], the structure of which has been determined crystallographically.

  通过顺序生成氮-碳和碳-碳键，以及一个电化学的钼-氮键断裂步骤，确定了一条从钼氮化物trans-[MoCl(N)(Ph2PCH2CH2PPh2)2]到甘氨酸和丙氨酸的甲基酯的合成路径，其中一个关键中间体是金属氮烯trans-[MoCl(NCHCO2Me)(Ph2PCH2CH2PPh2)2]，其结构已通过晶体学方法确定。
• Mechanism of ammonia formation by reaction of trans-[Mo(NH)X(Ph2PCH2CH2PPh2)2]+(X = F, Cl, Br, or I) with base in methanol
  作者：Richard A. Henderson、Geoffrey Davies、Jonathan R. Dilworth、Roger N. F. Thorneley

  DOI：10.1039/dt9810000040

  日期：——

  of [MoN(dppe)2]+ and X–. This cation reacts with methoxide ion (k= 1.7 ± 0.4 × 106 dm3 mol–1s–1), to yield [MoN(OCH3)(dppe)2] which rapidly abstracts a proton from solvent to give [Mo(NH)(OCH3)(dppe)2]+. When X = F, the same sequence of reactions occurs but dissociation of fluoride from the intermediate [Mo(N)F(dppe)2] is rate-limiting (k= 1.78 s–1). The pKa of trans-[Mo (NH)X(dppe)2]+ is very sensitive

  在甲醇中的环境温度下，反式-[[Mo（NH）X（dppe）2 ] + [其中X = F，Cl，Br或I且dppe = 1,2-双（二苯基膦基）乙烷]络合物对酸呈惰性，但用甲醇盐处理可高产氨。底物的初始快速去质子化使反式卤化物不稳定，并且当X = Cl，Br或I时，卤化物迅速释放（k > 300 s –1）以产生常见的物质，根据分光光度法的证据是该物质的平衡混合物。接触和溶剂分离的[MoN（dppe）2 ] +和X –离子对。该阳离子与甲醇离子反应（k= 1.7±0.4×10 6 dm 3 mol –1 s –1），得到[MoN（OCH 3）（dppe）2 ]，它可以从溶剂中快速提取质子，得到[Mo（NH）（OCH 3）（dppe） ）2 ] +。当X = F时，发生相同的反应顺序，但氟化物从中间体[Mo（N）F（dppe）2 ]的解离是限速的（k = 1.78 s –1）。该p ķ一个的反式-
• Ligand-centred chemistry of molybdenum organoimides. Formation of C–C bonds via generation of nitrogen ylides, stereospecific conversion of an allylimide into alkylvinyl-imides, liberation of cyanoformate or amino acid esters
  作者：Shirley A. Fairhurst、David L. Hughes、Saad K. Ibrahim、Marie-Laurence Abasq、Jean Talarmin、M. Arlete Queiros、Antonio Fonseca、Christopher J. Pickett

  DOI：10.1039/dt9950001973

  日期：——

  The range of imides trans-[MoCl(NCHR(1)R(2))(dppe)(2)](+) made from the nitride trans-[MoCl(N)(dppe)(2)] (dppe = Ph(2)PCH(2)CH(2)PPh(2), R(1) = H or organic group, R(2) = organic group) has been extended; deprotonation of the imide group at the alpha-carbon gives reactive alkenylamides which have nitrogen ylide character Mo=N+-C(-)HR} and these are attacked by electrophiles. Stepwise C-1 homologation of a methylimide to ethyl- and isopropyl-imides can be achieved by successive deprotonation and methylation steps. The crystal structure of the alkenylamide trans-[MoCl(NCHCO(2)Me)(dppe)(2)] has been determined, as has that of the imide produced directly from it by C-methylation, trans [MoClNCH(Me)CO(2)Me}(dppe)(2)](+). Deprotonation at the alpha-carbon of an allylimide complex gives a species which is regioselectively and stereospecifically attacked by electrophiles at the gamma-carbon; when the electrophile is the proton the overall reaction corresponds to a 1,3-prototropic rearrangement of the allylimide to the E-methylvinylimide. Electroreduction of imides in the presence of a source of protons releases the free amine; in this way esters of the amino acids glycine and DL-alanine have been:synthesised. Two protons-can be removed by base from imides with electron-withdrawing ester substituents and free cyanoformate esters are released from-the metal centre by substitution with dinitrogen or CO.