trans-[MoCl(N=CHCH=CH2)(dppe)2] | 204908-17-8

• 英文名称: trans-[MoCl(N=CHCH=CH2)(dppe)2]
• CAS: 204908-17-8
• 化学式: C₅₅H₅₂ClMoNP₄
• 分子量: 982.313
• InChiKey: MJEWPBYDQNKBGP-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  trans-[MoCl(N=CHCH=CH2)(dppe)2] 在 (CH₃)3COK 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Electrochemical dehydrodimerisation of a vinylenylamide ligand: formation of the binuclear group {MoN+CHCHCHCHCHCHN+Mo} which displays very strong electronic coupling in the {(MoIII)–(MoIV)} mixed-valence state

  摘要：

  Electrochemical dehydrodimerisation of an {Mo–NCHCHCH2} group gives an all-trans-{N+CHCHCHCHCHCHN+} ligand, bridging two MoIV centres; the {(MoIII)–bridge–(MoIV)} mixed-valence state is accessible by electrochemical reduction and exhibits very strong electronic coupling over the 11.7 Å which separates the two metal centres; this accords with EHMO calculations which show that the SOMO has substantial (30%) bridging-ligand character; in its capacity to function as a molecular wire linking two metal centres, the eight-atom hexatriene di(imide) chain {N(CH)6N} compares favourably with C8 chains of acetylenic carbons bridging other metal centres.

  DOI：

  10.1039/a800419f
• 作为产物：
  描述：

  trans-[MoCl(NCH=CHMe)(dppe)2](1+) 以 四氢呋喃 为溶剂， 生成 trans-[MoCl(N=CHCH=CH2)(dppe)2]
  参考文献：
  名称：

  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

  摘要：

  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 [MoCl{NCH(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.

  DOI：

  10.1039/dt9950001973