(t)BuC(N(t)Bu)2GaMe2 | 251292-88-3

• 英文名称: (t)BuC(N(t)Bu)2GaMe2
• CAS: 251292-88-3
• 化学式: C₁₅H₃₃GaN₂
• 分子量: 311.163
• InChiKey: FMGDEUOKYKCKNQ-UHFFFAOYSA-N

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：

  (t)BuC(N(t)Bu)2GaMe2 、 三苯碳四(五氟苯基)硼酸盐 以 further solvent(s) 为溶剂， 生成 、 1,1,1-三苯乙烷
  参考文献：
  名称：

  Synthesis and Structures of Cationic Aluminum and Gallium Amidinate Complexes

  摘要：

  Aluminum and gallium amidinate complexes, {RC(NR')(2)}MMe2 (R, R' = alkyl; M = Al, Ga), react with the "cationic activators" [Ph3C][B(C6F5)(4)] and B(C6F5)(3) to yield cationic Al and Ga alkyl species whose structures are strongly influenced by the steric properties of the amidinate ligand. The reaction of acetamidinate Al complexes {MeC(NR')(2)}AlMe2 (R' = Pr-i, 1a; R' = Cy, 3a) with 0.5 equiv of [Ph3C][B(C6F5)(4)] or B(C6F5)(3) yields {MeC(NR')(2)}(2)Al2Me3+ (R' = Pr-i, 2a(+); R' = Cy, 4a(+)) as the B(C6F5)(4)(-) or MeB(C6F5)(3)-salts. X-ray crystallographic analyses establish that 2a(+) and 4a(+) are double-amidinate-bridged dinuclear cations, in which the two metal centers are linked by mu-eta(1),eta(1) and mu-eta(1),eta(2) amidinate bridges. NMR studies show that 2a(+) undergoes two dynamic processes in solution: (i) a mu-eta(1),eta(1)/mu-eta(1),eta(2) amidinate exchange and (ii) Me exchange between the two metal centers. The reaction of {MeC((NPr)-Pr-i)(2)}GaMe2 (1b) with 0.5 equiv of B(C6F5)(3) yields {MeC((NPr)-Pr-i)(2)}(2)Ga2Me3+ (2b(+)), whose structure and dynamic properties are similar to those of 2a(+). The reaction of the bulkier 'Bu-substituted amidinate complexes {'BuC((NPr2)-Pr-i)(2)}MMe2 (M = Al, 6a; M = Ga, 6b) with 0.5 equiv of [Ph3C][B(C6F5)(4)] yields {'BuC((NPr)-Pr-i)(2)}MMe2.{'BuC((NPr)-Pr-i)(2)}MMe2 (M = Al, 7a(+); M = Ga, 7b(+)) as the B(C6F5)4- salts, the former of which is thermally unstable. An X-ray crystallographic analysis establishes that 7b(+) is a single-amidinate-bridged dinuclear cation, in which the two metal centers are linked by a mu-eta(1),eta(2) amidinate bridge. NMR data establish that the structures of 7a(+) and 7b(+) are similar and both species are rigid in solution. 6a and 6b also react with B(C6F5)(3) to yield [7a][MeB(C6F5)(3)] and [7b][MeB(C6F5)(3)], respectively, which decompose by C6F5- transfer- to yield {'BuC((NPr)-Pr-i)(2)}M(Me)(C6F5) (M = Al, 9a; M = Ga, 9b) and boron species. The "super-bulky" amidinate complexes {'BuC((NBu)-Bu-i)(2)}MMe2 (M = Al, 12a; M = Ga, 12b) react with 1 equiv of [Ph3C][B(C6F5)(4)] to yield {'BuC((NBu)-Bu-i)(2)}MMe+ (M = Al, 13a(+); M = Ga, 13b(+)) as the B(C6F5)(4)(-) salts. The salts [13a][B(C6F5)(4)] and [13b][B(C6F5)(4)] are thermally unstable and could not be isolated. However, the NMR data for 13a(+) and 13b(+) in C6D5Cl are consistent with base-free, three-coordinate structures or labile. four-coordinate solvated cations.These results provide a starting point for understanding the mechanism and reactivity trends in ethylene polymerization catalyzed by cationic Al amidinate species.

  DOI：

  10.1021/ja992104j
• 作为产物：
  描述：

  N,N′-二叔丁基碳二亚胺 、 甲基氯化镁 、 叔丁基锂 、 氯化镓 以 四氢呋喃 、 乙醚 为溶剂， 以45%的产率得到(t)BuC(N(t)Bu)2GaMe2
  参考文献：
  名称：

  Sterically Crowded Gallium Amidinate Complexes

  摘要：

  The sterically crowded gallium amidinate complexes {(BuC)-Bu-t(NR')(2)}GaX2 (X = Cl, Me, Et, CH2Ph; R' = Pr-i, Cy, Bu-t) have been synthesized in good yield. X-ray crystallographic analyses show that the steric interactions between the tBu and R' groups influence the R'-N-Ga angle and the steric environment at gallium.

  DOI：

  10.1021/om990472q