tetrakis(dimethylamido)hafnium | 19962-11-9

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机铪、汞、银、铂等
• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: tetrakis(dimethylamido)hafnium
• 英文别名: Hf(dimethylamide)₄；Hf(NMe2)4；Hf(DMA)4；dimethylazanide;hafnium(4+)
• CAS: 19962-11-9
• 化学式: 4C₂H₆N*Hf
• 分子量: 354.795
• InChiKey: QAGZBBYDOPNGNW-UHFFFAOYSA-N

物化性质

• 熔点：
  26-29 °C(lit.)
• 沸点：
  85°C 0,1mm
• 密度：
  1,4 g/cm3
• 闪点：
  109 °F

计算性质

• 辛醇/水分配系数(LogP)：
  0.62
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• TSCA：
  No
• 危险品标志：
  F,C
• 安全说明：
  S26,S36/37/39,S43,S45,S6
• 危险类别码：
  R11,R14,R34
• WGK Germany：
  3
• 海关编码：
  2924199090
• 危险品运输编号：
  UN 3396 4.3/PG 2

反应信息

• 作为反应物：
  描述：

  二硫化碳 、 tetrakis(dimethylamido)hafnium 生成
  参考文献：
  名称：

  在中等温度下使用单相分子前驱体合成 BaZrS3 和 BaHfS3 硫族化物钙钛矿薄膜

  摘要：

  我们开发了一种单相溶液处理方法，可在 575 °C 的温度下以短至 20 分钟的硫化时间生成 BaZrS 3和 BaHfS 3薄膜。为了制造分子前体油墨，我们利用已知的二硫化碳插入化学来合成第 4 族金属二硫代氨基甲酸盐，并扩展这种化学以创造以前没有报道过的物质，例如二硫代羧酸钡。

  DOI：

  10.1002/anie.202301049
• 作为产物：
  描述：

  lithium dimethylamide 、 氯化铪 反应 0.5h， 生成 tetrakis(dimethylamido)hafnium
  参考文献：
  名称：

  Organometallic compound, its synthesis method, and solution raw material and metal-containing thin film containing the same

  摘要：

  本发明的有机金属化合物是一种具有金属原子与氮原子之间的键或半金属原子与氮原子之间的键的化合物，该化合物中氯的含量为200 ppm或更低，水的含量为30 ppm或更低。此化合物的一般式由以下式（1）表示：M[(R1)2N](n−s)(R2)s(1)其中，M代表金属原子或半金属原子，金属原子为Hf、Zr、Ta、Ti、Ce、Al、V、La、Nb或Ni，半金属原子为Si，R1代表甲基基团或乙基基团，R2代表乙基基团，n代表M的化合价，s代表0到n-1之间的整数。

  公开号：

  US20040210071A1

文献信息

• Diamidophosphines with six-membered chelates and their coordination chemistry with group 4 metals: development of a trimethylene-methane-tethered [PN₂]-type “molecular claw”
  作者：S. Batke、T. Kothe、M. Haas、H. Wadepohl、J. Ballmann

  DOI：10.1039/c5dt04911c

  日期：——

  six-membered N–C3–P chelates was explored with group 4 metals, which allowed for the consecutive development of a new trimethylene-methane-tethered [PN2] scaffold. In the case of the propylene-linked system pr[NPN]H2, access to the sparingly soluble dibenzyl derivative pr[NPN]ZrBn2 (3-Zr) was gained, while thermally sensitive zirconium and hafnium diiodo complexes bn[NPN]MI2 (5-M, M = Zr, Hf) were isolated in

  膦束缚二酰胺基膦配体PhP（CH 2 CH 2 CH 2 NHPh）2（pr [NPN] H 2）和PhP（1,2-CH 2 -C 6 H 4 -NHSiMe 3）2（bn）的配位化学[NPN] H 2）具有六元N–C 3 –P螯合物，并与第4组金属进行了探索，从而可以连续开发新的由三亚甲基甲烷系留的[PN 2 ]支架。在丙烯连接的体系中，pr [NPN] H 2，获得了难溶的二苄基衍生物pr [NPN] ZrBn 2（3-Zr）的途径，而分离出了热敏感的锆和ha二碘配合物bn [NPN] MI 2（5-M，M = Zr，Hf）。亚苄基衍生物bn [NPN] H 2的情况。尽管这两个配体都有相关的膦链连接骨架结构，但发现它们的第4组络合物显示出C 1对称（bn [NPN] MX 2）或平均C S对称（pr [NPN] MX 2）中的结构。为了限制这些系统的整体灵活性，从而控制所得配合物的性
• Group IV Organometallic Compounds Based on Dianionic “Pincer” Ligands: Synthesis, Characterization, and Catalytic Activity in Intramolecular Hydroamination Reactions
  作者：Lapo Luconi、Andrea Rossin、Alessandro Motta、Giulia Tuci、Giuliano Giambastiani

  DOI：10.1002/chem.201203644

  日期：2013.4.8

  contributed to highlight the non‐innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as‐prepared bis‐amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate

  通过最简单方便的直接金属诱导的C芳基制备了由不对称双阴离子N，C，N'钳型配体稳定的Zr IV和Hf IV二酰胺配合物H键活化。简单的配体修饰有助于突出供体原子在控制环金属化动力学中所起的非清白作用。发现制备的双氨基催化剂是伯氨基烯烃的分子内加氢胺化/环化的良好候选者。这些化合物有效地促进这种催化转化的能力（通过在某些情况下提供快速和完全的底物转化）构成了朝着催化体系迈出的重要一步，该催化体系可以在相对较低的催化剂负载量和较温和的反应条件下运行。动力学研究和底物范围研究，以及对实际系统的初步DFT计算，
• High-<i>k</i> properties of atomic-layer-deposited HfO2 films using a nitrogen-containing Hf[N(CH3)2]4 precursor and H2O oxidant
  作者：Moonju Cho、Hong Bae Park、Jaehoo Park、Suk Woo Lee、Cheol Seong Hwang、Gi Hoon Jang、Jaehack Jeong

  DOI：10.1063/1.1637128

  日期：2003.12.29

  were deposited on HF-dipped Si wafers at 300 °C using an atomic-layer-deposition technique with N-containing Hf[N(CH3)2]4 and H2O as the precursor and oxidant, respectively. A thin interfacial SiNx layer was spontaneously formed at the HfO2/Si interface during film growth. This interfacial SiNx layer prevented substrate Si diffusion into the HfO2 film. Therefore, the reduction in the capacitance density

  使用原子层沉积技术在 300 °C 下将 HfO2 薄膜沉积在 HF 浸渍的 Si 晶片上，分别以含 N 的 Hf[N(CH3)2]4 和 H2O 作为前体和氧化剂。在薄膜生长过程中，在 /Si 界面处自发形成薄的界面 SiNx 层。该界面 SiNx 层阻止了衬底 Si 扩散到 膜中。因此，由于在 800 °C 下进行后退火而导致的电容密度降低被最小化。由于薄膜的非晶状结构，漏电流密度也降低了。此外，从电容等效厚度为 1.8 nm 的沉积膜中获得了在中带隙能态附近 <5×1010 cm-2 eV-1 的界面陷阱密度 (Dit)。该 Dit 值与生长良好的 SiO2/Si 界面相当。然而，
• Synthesis and Characterization of Group 4 Amido Silyl Complexes Free of Anionic π-Ligands
  作者：Zhongzhi Wu、Jonathan B. Diminnie、Ziling Xue

  DOI：10.1021/ic980821t

  日期：1998.11.1

  A series of early-transition-metal silyl complexes free of anionic pi-ligands such as cyclopentadienyl (Cp = eta(5) C5H5) have been synthesized. These Cp-free complexes (Me2N)(3)MSi(SiMe3)(3) [M = Zr (1), Hf (2)], (Me2N)(3)-TiSiPh2But (3), (Me2N)(3)ZrSiPh2But. 0.5THF (4), (Me2N)(3)HfSiPh2But. nTHF [n = 0.5 (5a), 1 (5b)], and (Me2N)(2)[(Me3Si)(2)N]ZrSiR3 [SiR3 = Si(SiMe3)(3) (7), SiPh2But (8)] were prepared by metathetic reactions of chloro triamido complexes (Me2N)(3)MCl (M = Ti, Zr, Hf) or (Me2N)(2)[(Me3Si)(2)N]ZrCl (6) with silyllithium reagents Li(THF)(3)Si(SiMe3)(3) or Li(THF)(3)SiPh2But. The structures of i, 3, 4, 5b, and 8 have been determined by X-ray crystallography and show that i, 3, and 8 adopt a distorted tetrahedral coordination geometry while 4 and 5b have a distorted trigonal bipyramidal geometry around the metal. The unit cell parameters are as follows. 1: space group R3c, a = 15.505(2) Angstrom, c = 19.308(4) Angstrom, V = 4019.9(13) Angstrom(3), Z = 6. 3: space group P2(1), a = 8.633(5) Angstrom, b = 14.790(7) Angstrom, c = 9.388(3) Angstrom, beta = 92.44(4)degrees, V = 1197.6(10) Angstrom(3), Z = 2. 4: space group Pbca, a = 16.538(9) Angstrom, b = 17.282(7) Angstrom, c = 18.566(8) Angstrom, V = 5306(4) Angstrom(3), Z = 8. 5b: space group Pna2(1), a = 17.463(6) Angstrom, b = 9.453(3) Angstrom, c = 17.800(6) Angstrom, V= 2938(2) Angstrom(3), Z = 4. 8: space group Pca2(1), a 19.775(5) Angstrom, b = 10.182(2) Angstrom, c = 15.752(5) Angstrom, V = 3172(2) Angstrom(3), Z = 4. The M-Si bond distances for i, 3, 1, 5b, and 8 are 2.781(2), 2.635(2), 2.803(2), 2.807(4), and 2.860(2) Angstrom, respectively. The Zr-Si bond in 8, to our knowledge, is the longest reported Zr-Si bond.
• New Titanium and Hafnium Complexes Bearing [⁻NNN^–] Pyrrolylpyridylamido Ligands as Olefin Polymerization Catalysts
  作者：Gang Li、Marina Lamberti、Giuseppina Roviello、Claudio Pellecchia

  DOI：10.1021/om300519s

  日期：2012.10.8

  Four new complexes bearing either unsubstituted or substituted pyrrolylpyridylanilido ligands, with the general formula [-NNN-]M(NMe2)(2) (M = Ti(IV), Hf(IV)), were synthesized and fully characterized by NMR spectroscopy and elemental analyses. The solid-state structures of one Ti and one Hf complex (both bearing the 2-isopropylphenyl substituent on the carbon bridging the pyridine and the aniline moieties) were obtained by single-crystal X-ray diffraction analyses, showing in both cases slightly distorted square pyramidal geometries, with the [-NNN-] ligand and one Me2N forming the base plane and the second Me2N as the apex. The new complexes and, for comparison, their zirconium analogues were tested as precatalysts for olefin polymerization, after activation with (AlBu2H)-Bu-i/methylalumoxane. Polymerization of ethylene under mild conditions (25 degrees C and 1 atm) was promoted by all catalysts with high activities, resulting in highly linear polyethylenes with ultrahigh molecular weights (M-w to 2.7 MDa). Polymerization of propylene (at 25 degrees C and 6 atm) was promoted by all complexes, with activities decreasing in the order Ti > Zr > Hf for the C-s-symmetric complexes and in the order Zr >> Ti > Hf for the C-1-symmetric complexes. Concerning stereoselectivity, catalysts based on Zr and Hf complexes behave similarly, with the C-1-symmetric species of both metals affording much more isotactic polymers than the C-5-symmetric species ([mmmm] 95% vs 73-79%) and performing better also in terms of activities and production of high-molecular-weight polypropylenes (M-w to 1.8 MDa for He. The Ti-based catalysts are less stereospecific and produce polypropylenes having very high molecular weights and rather broad molecular weight distributions. Solvent extraction of the raw samples showed the presence, in both cases, of an isotactic and an atactic fraction, also having different regioerrors, suggesting the formation of at least two active species.