Lithium, mol. (Li2) → HCID 131723810, compound

HRID 1862077Notes

Reaction equation

HRID 1862077 reaction equation
[Li]CCCC.[Li][Li].[Cl-:8].[Cl-].[Cl-].[Cl-].[Zr+4:12].[Li].[Li].[CH:15]1([C:20]([CH:30]2[CH:34]=[CH:33][CH:32]=[CH:31]2)([CH2:22][CH2:23][CH2:24][O:25][Si:26]([CH3:29])([CH3:28])[CH3:27])[CH3:21])[CH:19]=[CH:18][CH:17]=[CH:16]1>CCCCCC.C1(C)C=CC=CC=1>[Cl-:8].[Cl-:8].[Zr+2:12].[CH:30]1([C:20]([CH:15]2[CH:16]=[CH:17][CH:18]=[CH:19]2)([CH2:22][CH2:23][CH2:24][O:25][Si:26]([CH3:28])([CH3:27])[CH3:29])[CH3:21])[CH:31]=[CH:32][CH:33]=[CH:34]1

Participants

7

Reactant 4

HCID 139759Lithium, mol. (Li2)2×HCID 9856075Zirconium chloride (ZrCl4), (T-4)-2×HCID 131723811HCID 131723811, compoundHCID 178418339Butyllithium

Product 1

HCID 131723810HCID 131723810, compoundYield 22%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8058HexaneSolvent2×

Procedure

The previously distilled ligand (20.2 g, 0.07 mol) was placed in a 500 ml Schlenk flask and dissolved in dry hexane (250 ml). n-BuLi 1.6 M in hexane (87.3 ml 0.14 mol) was dropwise added is solution at 5° C. The resulting white suspension was heated to 75° C. for a 6 h period until the total formation of the dilithium salt was confirmed by NMR. The mixture was left to cool down to room temperature, filtered and dried under vacuum. ZrCl4 (16.28 g, 0.07 mol) was placed in the 500 Schlenk flask and toluene (200 ml) was added, and, at the same time, toluene (200 ml) was added to 2,2-bis(cyclopentadienyl)-5trimethylsiloxypentane dilithium salt. Both suspensions were cooled to −78° C. and the dilithium salt slurry was, via cannula, added to the ZrCl4 one. The resulting off-white suspension was allowed to warm to room temperature and stirred for 16 h. The resulting orange-red suspension was filtered and the cake washed with toluene (100 ml). The solvent was removed under vacuum and the resulting oily solid was repeatedly extracted with hexane, concentrated to 1/10 in volume and cooled to −30° C. to afford yellow crystals of the product (6.8 g, 22% yield). 1H NMR (CDCl3): Λ6.70 (C5H4, d, 4H), 5.82 (C5H4, d, 4), 3.75 (CH2, t, 2H), 2.28 (CH2, m, 2H), 1.83 (CH2, m, 2H), 1.80 (CH3, s, 3H), 0.18 ((CH3)3, s, 9H).

Workup

  1. customat 5° C
  2. waitThe mixture was left
  3. filtrationfiltered
  4. customdried under vacuum
  5. additionwas added
  6. temperatureBoth suspensions were cooled to −78° C.
  7. temperatureto warm to room temperature
  8. filtrationThe resulting orange-red suspension was filtered
  9. washthe cake washed with toluene (100 ml)
  10. customThe solvent was removed under vacuum
  11. extractionthe resulting oily solid was repeatedly extracted with hexane
  12. concentrationconcentrated to 1/10 in volume
  13. temperaturecooled to −30° C.

Sources & evidence

ORD record
ord-1009fc4ada674b5fba74eea3c0dfd827
Source dataset
uspto-grants-2003_03
Patent number
US06534665B1

Reaction notes

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