HCID 136331680, compound → HCID 136331682, compound

HRID 2088235Notes

Reaction equation

HRID 2088235 reaction equation
[Li]N([Si](C)(C)C)[Si](C)(C)C.[I:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]2[C:19]3[NH:23][C:22]([C:24]([C:61]4[CH:66]=[CH:65][C:64]([CH3:67])=[CH:63][CH:62]=4)=[C:25]4[N:60]=[C:28]([C:29]([C:53]5[CH:58]=[CH:57][C:56]([CH3:59])=[CH:55][CH:54]=5)=[C:30]5[NH:52][C:33](=[C:34]([C:40]6[CH:45]=[CH:44][C:43]([C:46]#C[Si](C)(C)C)=[CH:42][CH:41]=6)[C:35]6[CH:36]=[CH:37][C:38]=2[N:39]=6)[CH:32]=[CH:31]5)[CH:27]=[CH:26]4)=[CH:21][CH:20]=3)=[CH:14][CH:13]=1>COCCOCCOC>[I:11][C:12]1[CH:13]=[CH:14][C:15]([C:18]2[C:19]3[NH:23][C:22]([C:24]([C:61]4[CH:66]=[CH:65][C:64]([CH3:67])=[CH:63][CH:62]=4)=[C:25]4[N:60]=[C:28]([C:29]([C:53]5[CH:58]=[CH:57][C:56]([CH3:59])=[CH:55][CH:54]=5)=[C:30]5[NH:52][C:33](=[C:34]([C:40]6[CH:45]=[CH:44][C:43]([CH3:46])=[CH:42][CH:41]=6)[C:35]6[CH:36]=[CH:37][C:38]=2[N:39]=6)[CH:32]=[CH:31]5)[CH:27]=[CH:26]4)=[CH:21][CH:20]=3)=[CH:16][CH:17]=1

Participants

4

Reactant 2

HCID 136331680HCID 136331680, compoundHCID 178418261HCID 178418261, compound

Product 1

HCID 136331682HCID 136331682, compound

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent2×

Procedure

The following is a refined version of the standard procedure (Gross et al. (2001) Inorg. Chem., 40: 4762) designed to minimize exposure of the reaction mixture to moisture and air. A Schlenk flask was equipped with a reflux condenser and all essential inlets and outlets at the beginning of the procedure. A solution of CeI[N(SiMe3)2]2 was prepared in situ by reaction of CeI3 (75.0 mg, 0.144 mmol) and LiN(SiMe3)2 (288 μL, 0.288 mmol, 1.0 M in THF) in bis(2-methoxyethyl) ether (1.5 mL). This flask was not opened. A deaerated solution of porphyrin 12 (25.0 mg, 28.9 μmol) in bis(2-methoxyethyl) ether (1 mL) was added by syringe. The mixture was refluxed for 1 h, affording the metalated porphyrin as determined by UV/Vis. Then the double-decker complex (TTP)Eu(t-Bu4Pc) (45.2 mg, 28.9 μmol) was added. The mixture was refluxed for 6 h. After cooling to room temperature, chromatography [silica, toluene/hexanes (1:1), then CH2Cl2] gave three bands (green). The first and second band were combined and concentrated, affording a solid, which was further purified by SEC (THF), affording a brownish-green solid (40 mg, 54%): A 1H NMR spectrum was recorded, but the complexity due to the mixture of regioisomers prevented a complete interpretation. LD-MS obsd 2557.5 [M+], 2542.9, 2459.8, 2431.7 [M+-I]; FAB-MS obsd (LR) 2559.86, calcd exact mass 2559.72 (C147H123CeEuIN16Si); λabs363, 421, 425, 492, 560, 609 nm.

Workup

  1. customA Schlenk flask was equipped with a reflux condenser and all essential inlets and outlets at the beginning of the procedure
  2. customThis flask was not opened
  3. temperatureThe mixture was refluxed for 1 h

Sources & evidence

ORD record
ord-b305d41797394ba2b42415ad0a5fb9a3
Source dataset
uspto-grants-2004_04
Patent number
US06728129B2

Reaction notes

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