MoBr(1,4-(t)Bu2-1,3-diazabutadiene)(η-cycloheptatrienyl) | 214689-70-0

• 英文名称: MoBr(1,4-(t)Bu2-1,3-diazabutadiene)(η-cycloheptatrienyl)
• 英文别名: [MoBr(1,4-di-tert-butyl-1,3-diazabutadiene)(η-cycloheptatrienyl)]
• CAS: 214689-70-0
• 化学式: C₁₇H₂₇BrMoN₂
• 分子量: 435.259
• InChiKey: WDQOBTJPPNXDJZ-ASNJXXDOSA-M

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：

  4,4-二甲基-2-戊炔 、 MoBr(1,4-(t)Bu2-1,3-diazabutadiene)(η-cycloheptatrienyl) 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.25h， 以24%的产率得到[Mo(C=CBu^t)(1,4-^tBu₂-1,3-diazabutadiene)(η-C₇H₇)]
  参考文献：
  名称：

  Synthesis and redox chemistry of cycloheptatrienyl molybdenum carbon-chain complexes featuring diimine support ligands: [Mo{(CC)nCCR}(R′NCH–CHNR′)(η-C7H7)], (n = 0 or 1)

  摘要：

  The alkynyl complexes [Mo(C CR)(R'-dab)(eta-C7H7)] (dab diazabutadiene; R' = Bu-t, R = Ph, 2a; C6H4-4-Me, 3a; Bu-t, 4a; R' = C6H4--4-Me, R = Ph, 2b) have been synthesised by reaction of [MoBr(R'-dab)(eta-C7H7)] with LiC CR in thf. Crystallographic characterisation of [Mo(C CC6H4-4-Me)(Bu-t-dab)(eta-C7H7)], 3a determines a Mo-C-alpha bond distance of 2.154(3) angstrom. Cyclic voltammetric investigations on the alkynyl complexes 2a, 2b, 3a, 4a and the extended chain butadiynyl derivative [Mo(C CC CSiMe3)(Bu-t-dab)(eta-C7H7)], 5a, reveal that each complex exhibits a chemically and electrochemically reversible one-electron oxidation to give the corresponding 17-electron radical cation. Characterisation of the radicals [2a](+), [2b](+), [3a](+), and [5a](+) by IR and EPR spectroscopic techniques indicates that the redox process is strongly metal centred. Spectroscopic and synthetic investigations establish that 17-electron radicals of the type [Mo{(C C)(n)C CR)}(R'-dab)(eta-C7H7)](+) (n = 0 or 1) have relatively low thermodynamic stability. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.07.073
• 作为产物：
  描述：

  bromo(dicarbonyl)(η7-cyclopentatrienylium)molybdenum(0) 、 N,N'-二丁基-1,2-乙二亚胺 以 甲苯 为溶剂， 以81%的产率得到MoBr(1,4-(t)Bu2-1,3-diazabutadiene)(η-cycloheptatrienyl)
  参考文献：
  名称：

  Synthesis and redox properties of the cycloheptatrienylmolybdenum complexes [MoX(N–N)(η-C7H7)]z+, (N–N=2,2′-bipyridine or 1,4-But2-1,3-diazabutadiene; z=0, X=Br or Me; z=1, X=NCMe, CNBut or CO)

  摘要：

  The complexes [MoBr(N-N)(eta-C7H7)] (N-N = 2,2'-bipyridine (bipy), 1a; N-N = 1,4-Bu-2(t)-1,3-diazabutadiene (Bu-t-dab), (1b) have been prepared by reaction of [MoBr(CO)(2)(eta-C7H7)] with N-N in refluxing toluene. Treatment of 1a or 1b with MeLi affords [MoMe(N-N)(eta-C7H7)] (N-N = bipy or Bu-t-dab). The acetonitrile complexes [Mo(NCMe)(N-N)(eta-C7H7)][PF6], generated by reaction of [Mo(eta-C6H5Me)(eta-C7H7)][PF6] with N-N in NCMe, are precursors to [MoX(N-N)(eta-C7H7)][PF6] X = CNBut or CO; N-N = bipy or Bu-t-dab), through substitution of NCMe by X. Cyclic voltammetric studies reveal that each of the complexes [MoX(N-N)(eta-C7H7)](z+) (X = Me, Br, NCMe or CNBut; N-N = bipy or Bu-t-dab) exhibits a reversible one-electron oxidation and the 17-electron radicals derived from 1a, b and [Mo(CNBut)bipy)(eta-C7H7][PF6] have been isolated. E degrees values for the complexes [MoX(N-N)(eta-C7H7)](z+), demonstrate that in each case the bipy derivative is more easily oxidised than the corresponding Bu-t-dab analogue. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00708-6

文献信息

• Synthesis and structure of the diynyl complexes [Mo(CCCCR)L2(η-C7H7)], L2=chelate N- or P-donor ligand, R=SiMe3 or H: X-ray crystal structures of [Mo(CCCCSiMe3)(2,2′-bipyridine)(η-C7H7)] and [Mo(CCCCH)(Ph2PCH2CH2PPh2)(η-C7H7)]
  作者：Hannah N. Lancashire、Rezaul Ahmed、Tracy L. Hague (née Lumb)、Madeleine Helliwell、Gareth A. Hopgood、Leanne Sharp、Mark W. Whiteley

  DOI：10.1016/j.jorganchem.2006.05.011

  日期：2006.8

  [MoBr(N–N)(η-C7H7)] in thf affords the diynyl complexes [Mo(CCCCSiMe3)(N–N)(η-C7H7)], [1, N–N = 2,2′-bipyridine (bipy); 2, N–N  =1,4-Bu2t-1,3-diazabutadiene (But-dab)]; an analogous procedure yields [Mo(CCCCSiMe3)(CO)(PPh3)(η-C7H7)], 3 starting from [MoBr(CO)(PPh3)(η-C7H7)]. Replacement of bipy in complex 1 with Ph2PCH2CH2PPh2 (dppe) in refluxing toluene gives [Mo(CCCCSiMe3)(dppe)(η-C7H7)], 4. Proto-desilylation

  LiCCCCSiMe的反应3与[MoBr（Ñ - ñ）（η-C 7 H ^ 7）]在THF，得到二炔基配合物[沫（CCCCSiMe 3）（ñ - ñ）（η-C 7 H ^ 7）]，[ 1，N - N  ＝ 2，2′-联吡啶（联吡啶）；2，N - N  ＝ 1，4-Bu 2t -1，3-二氮杂丁二烯（Bu t -dab）]；类似的方法的产率[沫（CCCCSiMe 3）（CO）（PPH 3）（η-C 7 H ^ 7）]，3从[MoBr（CO）（PPH开始3）（η-C 7 H ^ 7）]。联吡啶在复杂的替换1的Ph 2 PCH 2 CH 2 PPH 2（DPPE）在回流的甲苯中给出[沫（CCCCSiMe 3）（DPPE）（η-C 7 H ^ 7）]，4。的原脱甲硅基2个4导致形成未取代的diynyls [沫（CCCCH）L- 2（η-C 7 H ^ 7）]（5，L 2  =卜吨-Dab; 6，L