Compound 4
(1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidine-2-ylidene)(2-(2,6-diisopropylphenyl)-3,3-dimethyl-2-azaspiro[4,5]decan-1-ylidene)beryllium
From: Neutral zero-valent s-block complexes with strong multiple bonding
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Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
Synthesis of [Be(MeL)(CyL)], 4: A solution of 2 (100 mg, 0.25 mmol, 1.0 eq.) in Et2O (5 mL) was treated with MeL (71 mg, 0.25 mmol, 1.0 eq.) and KC8 (67 mg, 0.5 mmol, 2.0 eq.), then stirred at room temperature for 8 h. The suspension was filtered over a pad of Celite® and the volume of the filtrate reduced in vacuo. Slow evaporation of the solution at –35 °C afforded 4 as a purple microcrystalline solid (37 mg, 24%). Single crystals suitable for X-ray diffraction could be obtained from benzene. M.p. 182 °C. 9Be NMR (Et2O, 56 MHz): δ = 32 (s). 1H NMR (THF-d8, 500 MHz): δ = 7.23–7.17 (m, 3H, CHAr), 7.14–7.13 (m, 3H, CHAr), 3.31–3.23 (m, 4H, C H (CH3)2), 1.87 (s, 1H, CH2), 1.80 (s, 3H, CH2), 1.59–1.46 (m, 2H, CH2,cy), 1.43 (d, JHH = 7 Hz, 3H, CH(C H3)2), 1.39 (d, JHH = 7 Hz, 9H, CH(C H3)2), 1.37–1.24 (m, 4H, CH2,cy), 1.23 (s, 3H, CH3), 1.22 (s, 6H, CH3), 1.22–1.15 (m, 1H, CH2,cy), 1.20 (s, 3H, CH3), 1.17 (d, JHH = 7 Hz, 9H, CH(C H3)2), 1.16 (d, JHH = 7 Hz, 3H, CH(C H3)2), 1.13–1.06 (m, 2H, CH2,cy),0.75 (brs, 6H, CH3), 0.43 (m, 1H, CH2,cy). 13C{1H} NMR (THF-d8, 125 MHz): δ = 191.9 (Cq,carbene), 189.3 (Cq,carbene), 150.7 (Cq), 150.3 (Cq), 140.0 (Cq), 139.8 (Cq), 128.2 (CHAr), 128.0 (CHAr), 126.0 (CHAr), 125.9 (CHAr), 69.8 (Cq), 57.4 (CH2), 52.5 (Cq), 49.7 (CH2), 47.7 (Cq), 41.2 (CH2,cy), 33.1 (CH3), 30.5 (CH3), 30.3 (CH2,cy), 30.1 (CH3), 29.0 (C H(CH3)2), 28.6 (CH( C H3)2), 25.1 (CH( C H3)2), 24.3 (CH2,cy). Elemental analysis calcd (%) for C43H66BeN2: C 83.30, H 10.73, N 4.52; found: C 81.24, H 10.84, N 3.92 (calcd (%) for [4–Et2O]: C 81.32, H 11.04, N 4.04). Crystal data for 4: C43H66BeN2, Mr = 619.98, red plate, 0.28×0.15×0.08 mm3, triclinic space group P , a = 10.205(3) Å, b = 11.905(3) Å, c = 16.885(4) Å, α = 95.186(7)°, β = 92.747(7)°, γ = 112.170(7)°, V = 1884.5(8) Å3, Z = 2, ρcalcd = 1.093 g ・ cm–3, μ = 0.061 mm–1, F(000) = 684, T = 100(2) K, R1 = 0.0882, wR2 = 0.1716, 7720 independent reflections [2θ≤52.742°] and 430 parameters.
