The Crystal Structure of [(Pyrene•−){Na+[(C2H5)2O]}]: A Model for Stacked Radical Anion Salts

✍ Scribed by Dipl.-Chem. Wolfgang Jost; Dipl.-Chem. Martin Adam; Priv.-Doz. Dr. Volker Enkelmann; Prof. Dr. Klaus Müllen

• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 269 KB
• Volume: 31
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.199208781

✦ Synopsis

Za-BPhh: Addition of a solution of iPrC=CH (0.30 mL, 3.0 mmol) in C,H,Br (6 mL) at -30 "C to a stirred mixture of [(C,H,),ZrMe,] (200 mg, 0.80 mmol) and [PhMe2NH][B(4-C,H,F),] (200 mg, 0.39 mmol), followed by warming to 25 'C, resulted in the deposition of a blue microcrystalline solid. Addition of hexane, followed by the recrystallization of the recovered solid from CH,CI,/ hexane, and drying in vacuo, afforded pure Za-BPh, (265 mg; 70%). Compounds 2b-BPhk and 2c-BPhk were obtained analogously; 2b-BPhk contains 10 % of cocrystallizing [(Cp,Zr),(p-Me){p-C=C(nPr)CH=C(nPr)(Me)}] + (shown by NMR spectroscopy and by the formation of H,C=C(nPr)CH=C-(nPr)(Me) with Hf), formed hy insertion of nPrCsCH into 3b; low solubility prevented recrystallization of 2c-BPh4. Selected 'H NMR data for cations (also see text). (300 MHz, CD,CI,, 25 "C): 1: 6 = 6.09, 5.92 (s, 10H; C,H,), 1.49, 1.29 (s, 9 H ; CMe,). (C,D,CI,, 25 "C): Za. 6 = 6.54 (s, 20H; C,H,), 0.82 (d, 6 H ; CHMe,), 0.39 (s. 3H; C=C(iPr)(Me)), -0.18 (sep, 1H: CHMe,). Zb: 6 = 6.54 (s, 20H; C,H,), 1.26 (m, 2H: CH,CH,CH,), 0.85 (t, 3H; CH,CH,CH,), 0.47 (s, 3H: C=C(nPr)(Me)), 0.44 (m, 2H; CH,CH,CH,), -1.14(~,3H;p-Me).Zc: 6 =6.63,6.29(s, lOH;C,H,), -1.lO(s,3H:p-Me).