Ti(NMe2)2(O-i-Pr)2 | 16530-80-6

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Ti(NMe2)2(O-i-Pr)2
• 英文别名: Dimethylazanide;propan-2-olate;titanium(4+)；dimethylazanide;propan-2-olate;titanium(4+)
• CAS: 16530-80-6
• 化学式: C₁₀H₂₆N₂O₂Ti
• 分子量: 254.209
• InChiKey: MZAVXIHDEWSJOT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.75
• 重原子数：
  15
• 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：
  48.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ti(NMe2)2(O-i-Pr)2 、 N,N-[[(2-methylpyridine)imino]di-1,2-ethandiyl]bis(4-methylbenzenesulfonamide) 以 二氯甲烷-D2 为溶剂， 生成 Ti((2-NC5H4)CH2N(CH2CH2NSO2Tol)2)(O-i-Pr2)2
  参考文献：
  名称：

  Sulfonamide-Supported Group 4 Catalysts for the Ring-Opening Polymerization of ε-Caprolactone and rac-Lactide

  摘要：

  Reaction of RCH2N(CH(2)CH(2)NHSO(2)Tol)(2) (R=2-NC5H4 (8,H2Lpy) or MeOCH2 (9, H2LOme)) with Ti(NMe2)(4) at room temperature afforded Ti(L-py)(NMe2)(2) (10) or Ti(L-OMe) (NMe2)(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding reactions With Ti((OPr)-Pr-i)(4) or Zr((OPr)-Pr-i)(4). (HOPr)-Pr-i required more forcing conditions to form the homologous bis(isopropoxide) analogues, M(L-R)((OPr)-Pr-i)(2) (M=Ti R=py (12) or OMe (14); M=Zr, R=py (13) or OMe (15)). Reaction of Ti(NMe2)(2)((OPr)-Pr-i)(2) with H2LR formed 12 or 14 under milder conditions. The X-ray structures of 10-15 have been determined revealing C-s symmetric, 6-coordinate complexes except for 13 which is 7-coordinate with one kappa(2)(N,O) bound sulfonamide donor. Compounds 10- 15 are all catalysts for the ring-opening polymerization (ROP) of epsilon-caprolactone, with the isopropoxide compounds being the fastest and best controlled, especially in the case of zirconium. In addition, Zr(L-OMe)((OPr)-Pr-i)(2) (15) was an efficient catalyst for the well-controlled ROP of rac-lactide both in toluene at 100 degrees C and in the melt at 130 degrees C, giving atactic poly(rac-lactide). The polymerization rates and control achieved for 13 and 15 are comparable to those of the well-established bis(phenolate)amine-supported Group 4 systems reported recently.

  DOI：

  10.1021/ic901524s
• 作为产物：
  描述：

  tetrakis(dimethylamido)titanium(IV) 、 [(tert-Bu)2Ga(μ-O(iso-Pr))]2 以 氘代苯 为溶剂， 生成 Ti(NMe2)2(O-i-Pr)2 、 [(tert-Bu)2Ga(μ-NMe2)]2
  参考文献：
  名称：

  Reaction of [Ga2(tBu)4(neol-H)]2 with early transition metal chlorides and amides

  摘要：

  The reaction of [Ga-2(Bu-t)(4)(neol-H)(2)] (neol-H-2 = 2,2-dimethylpropane-1,3-diol) with TiCl4, ZrCl4, or VCl4 in the presence of proton sponge, C10H6(NMe2)(2), yields [(Bu-t)GaCl3][C10H6(NMe2)(2)H] (1). The reaction of [Ga-2(Bu-t)(4)(neol-H)(2)] with M(NMe2)(4) (M = Ti, Zr) in yields [(Bu-t)(2)Ga(mu-NMe2)](2) (2) along with multiple transition metal containing products. In contrast, Cr(NEt2)(4) reacts with [Ga-2(Bu-t)(4)(neol-H)(2)] to yield [Ga-3(Bu-t)(5)(neol)(2)]. For the reaction with Ti(NMe2)(4), the identity of the titanium containing products have been determined as [(Bu-t)(2)Ga(neol)(2)Ti(NMe2)] (3), [Ti(NMe2)(2)(neol)(2)] (4) and [Ti(neol)(2)] (5). In addition, following the reaction by H-1 NMR allows for the observation of an additional gallium containing intermediate, [(Bu-t)(2)Ga(neol)(2)](2)Ti(NMe2)(2) (6) and [(Bu-t)(2)Ga](2)(mu-neol) (7). Compounds 4 and 5 are also made by the direct reaction of Ti(NMe2)(4) with neol-H-2. Reaction of Ga(Bu-t)(3) with HNMe2 yields (Bu-t)(3)Ga(HNMe2) (8). Compound 2 is also formed along with [Ti(NMe2)(2)((OPr)-Pr-i)(2)] (9) from the reaction of [(Bu-t)(2)Ga(mu-(OPr)-Pr-i)](2) with Ti(NMe2)(4). The formation of compound 6 is implied by the isolation of the hydration product, [(Bu-t)(2)Ga(neol)(2)Ti(mu-O)Ga(Bu-t)(HNMe2)] (10). The reaction of CpTi(NMe2)(3) with [(Bu-t)(2)Ga(neol-H)](2) yields [(Bu-t)(2)Ga(neol)(2)TiCp] (11) and 2. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(02)01267-6

文献信息

• Ligand Variations in New Sulfonamide-Supported Group 4 Ring-Opening Polymerization Catalysts
  作者：Andrew D. Schwarz、Katherine R. Herbert、Cristina Paniagua、Philip Mountford

  DOI：10.1021/om100508j

  日期：2010.9.27

  2-C6H10(NSO2Mes)2), and in situ generated isopropoxide initiators derived from 30−32 were investigated for the ROP of ε-caprolactone (ε-CL). The four-coordinate 25 was the most active, forming poly(ε-CL) with a relatively narrow PDI and well-controlled Mn. Compounds 22, 23, 25, and 26 and isopropoxides generated in situ from 30−32 were all active for the ROP of rac-lactide. Of these, the initiators based on Zr(N3RN)(CH2SiMe3)

  报道了范围广泛的磺酰胺负载的4族酰胺，烷基和醇盐配合物的合成，结构和开环聚合（ROP）能力，这些磺酰胺的N-取代基，金属，配位数和几何形状各不相同。Ti（NMe 2）4或Ti（NMe 2）2（O i Pr）2与MeOCH 2 CH 2 N（CH 2 CH 2 NHSO 2 Me）2（12，H 2 N 2 Ms N OMe）或PhCH的反应2 N（CH 2 CH2 NHSO 2 R）2（R = Tol（10，H 2 N 2 Ts N Ph）或Me（11，H 2 N 2 Ms N Ph））提供Ti（N 2 Ms N OMe）（NMe 2）2（18），Ti（N 2 Ts N Ph）（NMe 2）2（19），Ti（N 2 Ms N Ph）（NMe 2）2（20），Ti（N 2 Ms N OMe）（O i Pr）2（21），Ti（N 2 Ts N Ph）（O i Pr）2（22），Ti（N 2 Ms
• Structure and reactivity of [TiRu(CO)2(C5H5)(NMe2)3]: a direct early-late transition metal bond formed by amine elimination
  作者：William J. Sartain、John P. Selegue

  DOI：10.1021/ja00306a049

  日期：1985.10
• Synthesis and Crystal Structures of Bis(sulfonamido) Titanium Bis(alkoxide) Complexes:  Mechanistic Implications in the Bis(sulfonamide) Catalyzed Asymmetric Addition of Dialkylzinc Reagents to Aldehydes
  作者：Suzy Pritchett、David H. Woodmansee、Peter Gantzel、Patrick J. Walsh

  DOI：10.1021/ja973557w

  日期：1998.7.1
• Sulfonamide-Supported Group 4 Catalysts for the Ring-Opening Polymerization of ε-Caprolactone and <i>rac</i>-Lactide
  作者：Andrew D. Schwarz、Amber L. Thompson、Philip Mountford

  DOI：10.1021/ic901524s

  日期：2009.11.2

  Reaction of RCH2N(CH(2)CH(2)NHSO(2)Tol)(2) (R=2-NC5H4 (8,H2Lpy) or MeOCH2 (9, H2LOme)) with Ti(NMe2)(4) at room temperature afforded Ti(L-py)(NMe2)(2) (10) or Ti(L-OMe) (NMe2)(2) (11), respectively, which contain tetradentate bis(sulfonamide)amine ligands. The corresponding reactions With Ti((OPr)-Pr-i)(4) or Zr((OPr)-Pr-i)(4). (HOPr)-Pr-i required more forcing conditions to form the homologous bis(isopropoxide) analogues, M(L-R)((OPr)-Pr-i)(2) (M=Ti R=py (12) or OMe (14); M=Zr, R=py (13) or OMe (15)). Reaction of Ti(NMe2)(2)((OPr)-Pr-i)(2) with H2LR formed 12 or 14 under milder conditions. The X-ray structures of 10-15 have been determined revealing C-s symmetric, 6-coordinate complexes except for 13 which is 7-coordinate with one kappa(2)(N,O) bound sulfonamide donor. Compounds 10- 15 are all catalysts for the ring-opening polymerization (ROP) of epsilon-caprolactone, with the isopropoxide compounds being the fastest and best controlled, especially in the case of zirconium. In addition, Zr(L-OMe)((OPr)-Pr-i)(2) (15) was an efficient catalyst for the well-controlled ROP of rac-lactide both in toluene at 100 degrees C and in the melt at 130 degrees C, giving atactic poly(rac-lactide). The polymerization rates and control achieved for 13 and 15 are comparable to those of the well-established bis(phenolate)amine-supported Group 4 systems reported recently.
• Reaction of [Ga2(tBu)4(neol-H)]2 with early transition metal chlorides and amides
  作者：Laura H. van Poppel、Simon G. Bott、Andrew R. Barron

  DOI：10.1016/s0277-5387(02)01267-6

  日期：2003.1

  The reaction of [Ga-2(Bu-t)(4)(neol-H)(2)] (neol-H-2 = 2,2-dimethylpropane-1,3-diol) with TiCl4, ZrCl4, or VCl4 in the presence of proton sponge, C10H6(NMe2)(2), yields [(Bu-t)GaCl3][C10H6(NMe2)(2)H] (1). The reaction of [Ga-2(Bu-t)(4)(neol-H)(2)] with M(NMe2)(4) (M = Ti, Zr) in yields [(Bu-t)(2)Ga(mu-NMe2)](2) (2) along with multiple transition metal containing products. In contrast, Cr(NEt2)(4) reacts with [Ga-2(Bu-t)(4)(neol-H)(2)] to yield [Ga-3(Bu-t)(5)(neol)(2)]. For the reaction with Ti(NMe2)(4), the identity of the titanium containing products have been determined as [(Bu-t)(2)Ga(neol)(2)Ti(NMe2)] (3), [Ti(NMe2)(2)(neol)(2)] (4) and [Ti(neol)(2)] (5). In addition, following the reaction by H-1 NMR allows for the observation of an additional gallium containing intermediate, [(Bu-t)(2)Ga(neol)(2)](2)Ti(NMe2)(2) (6) and [(Bu-t)(2)Ga](2)(mu-neol) (7). Compounds 4 and 5 are also made by the direct reaction of Ti(NMe2)(4) with neol-H-2. Reaction of Ga(Bu-t)(3) with HNMe2 yields (Bu-t)(3)Ga(HNMe2) (8). Compound 2 is also formed along with [Ti(NMe2)(2)((OPr)-Pr-i)(2)] (9) from the reaction of [(Bu-t)(2)Ga(mu-(OPr)-Pr-i)](2) with Ti(NMe2)(4). The formation of compound 6 is implied by the isolation of the hydration product, [(Bu-t)(2)Ga(neol)(2)Ti(mu-O)Ga(Bu-t)(HNMe2)] (10). The reaction of CpTi(NMe2)(3) with [(Bu-t)(2)Ga(neol-H)](2) yields [(Bu-t)(2)Ga(neol)(2)TiCp] (11) and 2. (C) 2002 Elsevier Science Ltd. All rights reserved.