Second-harmonic generation properties of some co-ordination compounds based on pentanedionato ligands

Abstract

The synthesis and non-linear optical properties of pentanedionato ligands and their complexes with BF;, rhodium(1) and palladium(I1) are described. 4-Nitrobenzoylacetone 1 , 3-(2,4-dinitrophenyl)pentane-2,4-dione 3, and the BF; adduct difluoro(4-methoxyben+oylacetonato)boron 2, were used to synthesize a range of palladium(1r) and rhodium(1) complexes. The single-crystal X-ray structures of bis(triphenylphosphine)(4-nitrobenzoylacetonato) pal I ad i u m (11) te t r af I uoro bo r ate 4, and b is( t r i p h en y I p hosp h i ne) [ 3-( 2,4-d i nit rop hen y I )-pen tane-2,4-d i o nato] pa I I ad ium(I1) tetrafluoroborate 5, were determined. 4 and 5 crystallize in the triclinic space group f i , with two molecular units per unit cell with dimensions of a= 10.995(1) A, b= 13.692(3) A, c= 14.964(4) A, a=102.933(20)", B= 92.286( 16)", y=98.466( 14)" for 4, and a= 12.066(2) A, b= 12.112(2) A, c= 15.681(2) A, a = 103.840( 12)", B= 91.227( 12)", y=99.596( 14)" for 5. Both 4 and 5 have the pentanedionato oxygens directly bonded to the squareplanar Pd" atom, with Pd-0 bond lengths of 2.034(5) and 2.046(5) A for 4 and 2.019(2) and 2.033(2) A for 5. The phenyl ring in 4 is planar with the pentanedionato ring, but in 5 the phenyl group is perpendicular to the pentanedionato ring. The second-harmonic generation (SHG) properties of the compounds were measured and compared with those for urea.

13C NMR spectrum of crystalline [Rh(Acac) (CO)2]: A contribution to the discussion on [Rh(Acac) (CO)2] molecular structure in the solid state

“…This conclusion has been verified by the observation of the second harmonic generation (SHG) in a polycrystalline sample of 1 [45]. (It should be mentioned that in [14] no SHG from polycrystalline 1 has been observed).…”

Unprecedented C–C Bond Formation via Ipso Nucleophilic Substitution of 2,4-Dinitrobenzene Sulfonic Acid with Active Methylene Compounds

“…28 As a white solid (85 mg, 64% yield, mp 90− 92 °C); purification over a column of silica gel (10−15% EtOAc in hexane); 1 16 As a yellow crystalline (64 mg, 43% yield, mp 93−95 °C); purification over a column of silica gel (10−15% EtOAc in hexane); 1 30 As a yellow liquid (61 mg, 43% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 (Z)-3-(2,4-Dinitrophenyl)-4-hydroxypent-3-en-2-one (1i). 31 As a yellow liquid (53 mg, 40% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 H NMR (CDCl 3 , 500 MHz): δ 16.58 (s, 1H), 8.79 (d, 1H, J = 3.0 Hz), 8.50 (dd, 1H, J 1 = 2.5 Hz, J 2 = 8.5 Hz), 7.62 (d, 1H, J = 8.5 Hz), 1.86 (s, 6H); 13 32 As a yellow liquid (88 mg, 55% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 H NMR (CDCl 3 , 400 MHz): δ 8.33 (d, 1H, J = 2.0 Hz), 7.92 (dd, 1H, J 1 = 2.0 Hz, J 2 = 8.0 Hz), 7.73 (d, 1H, J = 8.4 Hz), 5.39 (s, 1H), 3.82 (s, 6H); 13 C{ 1 H} NMR (CDCl 3 , 100 MHz): δ 167.1, 149.0, 132.9, 131.8, 130.1 (q, J = 3.2 Hz), 124.1, 122.7 (q, J = 3.8 Hz), 121.4, 54.0, 53.6; 19 33 As a yellow liquid (92 mg, 53% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 H NMR (CDCl 3 , 400 MHz): δ 8.32 (d, 1H, J = 2.0 Hz), 7.89 (dd, 1H, J 1 = 2.0 Hz, J 2 = 8.0 Hz), 7.73 (d, 1H, J = 8.4 Hz), 5.34 (s, 1H), 4.28 (dq, 4H, J 1 = 2.0 Hz, J 2 = 7.2 Hz), 1.29 (t, 6H, J = 7.2 Hz); 13 C{ 1 H} NMR (CDCl 3 , 100 MHz): δ 167.8, 149.1, 132.8, 132.1, 130.0 (q, J = 3.5 Hz), 124.1, 122.7 (q, J = 3.9 Hz), 121.5, 62.9, 54.4, 14.2; 19 34 As a yellow liquid (100 mg, 53% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 35 As a yellow liquid (62 mg, 39% yield); purification over a column of silica gel (10−15% EtOAc in hexane); 1 H NMR (CDCl 3 , 500 MHz): δ 13.06 (s, 1H), 8.24 (d, 1H, J = 2.0 Hz), 7.83 (dd, 1H, J 1 = 2.0 Hz, J 2 = 8.0 Hz), 7.47 (d, J = 8.0 Hz, 1H), 4.23−4.17 (m, 1H), 4.06−3.99 (m, 1H), 1.87 (s, 3H), 1.10 (t, J = 7.0 Hz, 3H); 13 C{ 1 H} NMR (CDCl 3 , 125 MHz): δ 174.1, 170.6, 149.9, 135.2, 134.1, 131.4, 131.1, 129.3 (q, J = 3.4 Hz), 124.1, 121.9 (q, J = 4.0, Hz), 100.3, 61.4, 20.0, 13.9; 19…”