lithium N,N'-diphenylformamidinate

• 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: lithium N,N'-diphenylformamidinate
• 英文别名: N,N'-diphenylformamidinyl lithium；lithium;phenyl(phenyliminomethyl)azanide
• 化学式: C₁₃H₁₁LiN₂
• 分子量: 202.185
• InChiKey: FQLZJVZRLHUWGK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.06
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  13.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  lithium N,N'-diphenylformamidinate 、 以 乙腈 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Chisholm, Malcolm H.; Cotton, F. Albert; Daniels, Lee M., Journal of the Chemical Society, Dalton Transactions

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N'-二苯甲脒 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以54%的产率得到lithium N,N'-diphenylformamidinate
  参考文献：
  名称：

  Cornelißen, Carsten; Erker, Gerhard; Kehr, Gerald, Zeitschrift fur Naturforschung, B: Chemical Sciences, 2004, vol. 59, # 11-12, p. 1246 - 1252

  摘要：

  DOI：

文献信息

• Formamidino birdged complexes of rhodium and iridium carbonyls
  作者：Edward W. Abel、Stephen J. Skittrall

  DOI：10.1016/s0022-328x(00)90299-7

  日期：1980.7

  Lithio-1,3-diarylformamidines undergo reaction with the carbonyl chlorides of rhodium and iridium [Rh(CO)2Cl}2] and [Ir(CO)3Cl], to yield the deep red formamidino bridges dimeric species [M(CO)2(CHNR}2)}2] (M = Rh, Ir).

  Lithio-1,3-二芳基甲am与铑和铱的羰基氯化物[Rh（CO）2 Cl} 2 ]和[Ir（CO）3 Cl]反应，生成深红色的甲酰胺基桥二聚体[M （CO）2（CH NR} 2）} 2 ]（M ＝ Rh，Ir）。
• Two new titanium complexes with N,N′-diphenylformamidinium (DPhF)−, Ti(DPhF)3 and Ti2(μ-DPhF)2(DPhF)2(μ-NPh)2
  作者：F.Albert Cotton、William A. Wojtczak

  DOI：10.1016/s0277-5387(00)81698-8

  日期：1994.5

  Abstract The reduction of TiCl4 with 1 equiv. of sodium amalgam and addition of 3 equiv. of [PhNC(H)NPh]Li affords the titanium(III) compound Ti(DPhF)3 (1). The molecular symmetry of 1 is slightly distorted from D3. Interestingly, reduction of TiCl4 with 2 equiv. of HSn(n-Bu)3 and addition of 3 equiv. of [PhNC(H)NPh]Li does not produce a TiII product, but rather an imido bridged compound, Ti2(μ-NPh)2(μ-DPhF)2(DPhF)2

  摘要TiCl4的还原当量为1。汞齐的钠和3当量的添加。制备[PhNC（H）NPh] Li可得到钛（III）化合物Ti（DPhF）3（1）。1的分子对称性与D3略有不同。有趣的是，将TiCl4还原为2当量。HSn（n-Bu）3的加法和3当量的加法。的[PhNC（H）NPh] Li不会产生TiII产物，而是亚氨基桥接的化合物Ti2（μ-NPh）2（μ-DPhF）2（DPhF）2，（2），其中亚氨基配体TiIV原子与TiIV原子形成短键[1.789（2）A]和长键[2.068（2）A]。从[DPhF]-离子生成NPh2-配体的过程尚未确定。但是，很明显，钛原子必须从+2氧化为+4，并且[DPhF]-配体中的CN键被裂解。报道了两种化合物的晶体结构。
• <i>nido</i>-Metalloborane Complexes:  Synthesis and Structural Characterization of μ₂,η⁴-Hexahydrodiboratotetrakis(<i>N</i>,<i>N‘</i>-diarylformamidinato)ditantalum(III), Aryl = <i>p</i>-Tolyl and Phenyl. The First Structurally Characterized Complexes Containing the μ₂,η⁴-B₂H₆^2- Ligand
  作者：F. Albert Cotton、Lee M. Daniels、Carlos A. Murillo、Xiaoping Wang

  DOI：10.1021/ja954087d

  日期：1996.1.1

  The nido-metalloborane complexes Ta-2(mu(2),eta(4)-B2H6)(DTolF)(4) . 2Et(2)O, 1, DTolF(-) = [(p-tolyl)NCHN(p-tolyl)](-), and Ta-2(mu(4)-B2H6)(DPhF)(4) . Et(2)O, 2, DPhF(-) = [phenylNCHNphenyl](-), are formed as the products of tantalum pentachloride with lithium borohydride followed by the addition of LiDTolF or LiDPhF. Complexes 1 and 2 are the first structurally characterized compounds in which two metal atoms that are bonded to each other are also bridged by an hexahydroborate ligand through four B-H-M three-center bonds in a symmetric bonding mode. The Ta-Ta distances are 2.725(1) Angstrom in 1 and 2.728(1), 2.736(1) Angstrom in 2. Crystallographic data are as follows: compound 1, P (1) over bar, a = 15.197(3) Angstrom, b = 15.675(2) Angstrom, c = 16.449(6) Angstrom, alpha = 102.50(1)degrees, beta = 99.04(1)degrees, gamma = 117.10(2)degrees, and Z = 2; compound 2, P (1) over bar with a = 11.547(5) Angstrom, b = 20.03(1) Angstrom, c = 29.934(8) Angstrom, alpha = 107.60(1)degrees, beta = 100.86(2)degrees, gamma = 95.65(2)degrees, and Z = 4. In these two molecules there are two ArNC(H)NAr- ligand coordinated in a chelating manner to each of two tantalum atoms. These two Ta(DTolF)(2) or Ta(DPhF)(2) fragments are united by a Ta=Ta bond (ca. 2.73 Angstrom), and a B2H6 unit lies across the bond forming two B-H-Ta bridge bonds to each tantalum atom. The B2H6Ta2 moiety constitutes a B2Ta2 nido-metalloborane, formally similar to B4H10.
• Metal-assisted unorthodox reactions of formamidines: coupling, cleavage and insertions
  作者：F.Albert Cotton、Lee M. Daniels、John H. Matonic、Xiaoping Wang、Carlos A. Murillo

  DOI：10.1016/s0277-5387(96)00366-x

  日期：1997.1

  The purpose of this report is to call attention to the wide range of reactions that an amidine or amidinium may undergo in the presence of reduced metal ions, other than simple ligation of the metal ions. Crystal structures of five examples are presented. In (eta-dmpm)Cl2Ta(mu-NTol)(mu-eta(2)-HC=NTol)(mu-dmpm)TaCl(eta(2)-DTolF) (I), both fragments from a C-N bond cleavage of the di-p-tolylformamidinate anion, DTolF(-), namely tolylimido and tolylformimidoyl groups, are found forming bridges between the metal atoms. An amido group is also found in TaCl2(NPh)(DPhF)(HDPhF) (II), in which a six-coordinated tantalum atom is surrounded also by two chlorine atoms, a chelating diphenylformamidinate, DPhF(-) and a neutral HDPhF molecule. A new neutral chelating ligand forms during the synthesis of CoCl2(PhNCHNPhCHNPh) (III), in which the divalent cobalt atom is in a pseudo-tetrahedral environment. The six-membered metallocycle formed by th Co-N-C-N-C-N atoms is essentially planar. Reaction of K with crude Ta-2(mu(2)-eta(4)-B2H6)(mu-DTolF)(4) produces [(B2H5)N(Tol)C(H)N(Tol)]Ta(mu(2)-NTol)(2)(mu(2)-DTolF)(2)Ta[(Tol)NC(H)N(Tol)B2H5]. 2Et(2)O (IV), in which a ditantalum unit is bridged by two DTolF and two tolylimido groups. A new ligand formed by fusion of a B2H5- unit to a DTolF(-) anion chelates to each of the metal atoms. In the crystals, 50% of the B2H5 moieties are BH3 groups. Coupling of two DPhF anions is observed in PhNC(H)N(Ph)C(H)(NPh)(2)Ta(DPhF)(3) . Et(2)O (V). The new dianion chelates the metal center, to which three other DPhF groups are attached giving an eight-coordinated compound. Copyright (C) 1997 Elsevier Science Ltd.
• Cleavage of Formamidinate Ligands on a TaTa Double Bond:  Formation of H<i>_x</i>CNAryl (<i>x</i> = 0 and 1) and Arylimido-Bridged Complexes
  作者：F. Albert Cotton、Lee M. Daniels、Carlos A. Murillo、Xiaoping Wang

  DOI：10.1021/ic9611507

  日期：1997.2.1

  Three complexes which resulted from the C-N bond cleavage reactions of formamidinate anions, [ArNC(H)NAr](-), have been synthesized and structurally characterized. The reaction of N,N'-diphenylformamidinate, DPhF(-), with (Me(2)S)Cl2Ta(mu-Me(2)S)(mu-Cl)(2)TaCl2(SMe(2)) (abbreviated as Ta2Cl6(SMe(2))(3)) in the presence of Zn metal produces the CNPh-containing dinuclear compound (eta(2)-DPhF)(2)Ta(mu-NPh)(mu-eta(2)-CNPh)Ta(eta(2)-DPhF)(2) . C7H8, 1 . C7H8. By using DTolF(-) and Na/Hg as reducing agent, the isolated product is (eta(2)-DTolF)Ta(mu-NTol)(mu-eta(2)-CNTol)(mu-DTolF)(2)Ta(eta(2)-DTolF) . 1.5C(6)H(14), 2 . 1.5C(6)H(14), where DTolF(-) = N,N'-di(p-tolyl)formamidinate. Both 1 and 2 are isolated in low yields. There is a formal single bond between the tantalum atoms which are bonded to intact formamidinate ions as well as the two fragments which result from the cleavage of a formamidinate ligand, namely arylimido (NAr2-) and (CNAr). In the absence of a reducing agent, the reaction of LiDTolF and Ta2Cl6(SMe(2))(3) produces Cl-2(eta(2)-DTolF)Ta(mu-NTol)(mu-eta(2), eta(2)-HCNTol)Ta(eta(2)-DTolF)(2), 3, in high yield. In addition to the tolylimido group, a tolylformimidoyl fragment (HCNTol) binds to the tantalum atom through both carbon and nitrogen atoms in a eta(2),eta(2) mode. Because of this and the relatively long C-N bond distance (1.42(1) Angstrom), the ligand can be formulated as [HCNTol](3-). Thus the tantalum atoms in 3 have a formal oxidation state of +5, which precludes the presence of a metal-metal bond. Crystal data for 1 . C7H8: monoclinic, I2/a, a = 19.437(2) Angstrom, b = 15.587(1) Angstrom, c = 20.401(1) Angstrom, and beta = 97.840(6)degrees. Crystal data for 2 . 1.5C(6)H(14): triclinic, , a = 13.990(2) Angstrom, b = 15.841(1) Angstrom, c = 19.442(4) Angstrom, alpha = 98.98(1)degrees, beta = 104.07(1)degrees; gamma = 109.59(1)degrees. Crystal data for 3: monoclinic, P2(1)/n, a = 17.962(3) Angstrom, b = 15.539(4) Angstrom, c = 19.973(3) Angstrom, beta = 90.126(7)degrees.