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11.
H.-J. Mai S. Wocadlo H.-C. Kang W. Massa K. Dehnicke C. Maichle-Mssmer J. Strhle D. Fenske 《无机化学与普通化学杂志》1995,621(5):705-712
Phosphanimine and Phosphoraneiminato Complexes of Iron. The Crystal Structures of [FeCl3(Me3SiNPEt3)], [FeCl2(Me3SiNPEt3)]2, [FeCl2(NPEt3)]2, and [Fe(O2C? CH3)2(NPEt3)]2 The phosphanimine complexes [FeCl3(Me3SiNPEt3)] (red-orange) and [FeCl2(Me3SiNPEt3)]2 (colourless) have been prepared by reactions of Me3SiNPEt3 with FeCl3 and FeCl2, respectively, in CH2Cl2 suspensions. Thermal decomposition of these donor-acceptor complexes in boiling toluene leads to the phosphoraneiminato complex [FeCl2(NPEt3)]2 (black), whereas [Fe(O2C? CH3)2(NPEt3)]2 (brown) is formed from iron(II) acetate and Me3SiNPEt3 in boiling acetonitrile. The complexes are characterized by IR spectroscopy and by crystal structure determinations. [FeCl3(Me3SiNPEt3)] (1) : Space group P21/c, Z = 8, structure determination with 4 673 unique reflections, R = 0.033. Lattice dimensions at ?15°C: a = 1 607.8, b = 1 602.0, c = 1 417.2 pm, β = 106.56°. 1 forms monomeric molecules with tetrahedrally coordinated iron atoms. Bond lengths in average: Fe? N = 196.9 pm, Fe? Cl = 219.7 pm. [FeCl2(Me3SiNPEt3)]2 (2) : Space group P21/c, Z = 4, structure determination with 4 992 unique reflections, R = 0.048. Lattice dimensions at 20°C: a = 1 457.9, b = 1 685.4, c = 1 507.3 pm, β = 116.74°. 2 forms dimeric molecules, which are associated by chloro bridges. The iron atoms are tetrahedrally coordinated with trans positions of the phosphanimine ligands. Both lengths in average: Fe? N = 202.2 pm, Fe? Clterminal = 224.7 pm, Fe? Cl bridge = 241.0 pm. [FeCl2(NPEt3)]2 (3): Space group P21/n, Z = 2, structure determination with 2763 unique reflections, R = 0.039. Lattice dimensions at ?70°C: a = 799.1, b = 1009.0, c = 1441.9 pm, β = 93.45°. 3 forms centrosymmetric dimeric molecules, in which the tetrahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands. Bond lengths in average: Fe? N = 191.4 pm, Fe? Cl = 222.7 pm. [Fe(O2C? CH3)2(NPEt3]2 (4): Space group P21/n, Z = 2, structure determination with 3005 observed unique reflections, R = 0.034. Lattice dimensions at -65°C: a = 886.4, b = 1444.6 pm, β = 90.60°. 4 forms centrosymmetric dimeric molecules, in which the octahedrally coordinated iron atoms are associated by the nitrogen atoms of the phosphoraneiminato ligands with bond lengths Fe? N of 191.9 and 195.0 pm. The acetate groups are coordinated in a chelating fashion. 相似文献
12.
Acyl- and Alkylidenephosphines. XXII. Synthesis and Structure of 1, 3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane At ?30°C methylbis(trimethylsilyl)phosphine reacts with carbon disulfide to give a red adduct first which rearranges to [bis(trimethylsilylsulfano)methylidene]methylphosphine 1a . In contrast to the thermally stable phenyl derivative 1b [2], this compound with its insufficiently shielded P?C group dimerizes fast with increasing temperature. 1,3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane 2a formed by this reaction, crystallizes in the triclinic space group P1 with following dimensions of the unit cell, determined at a temperature of measurement of ?80 ± 3°C: a = 1024.7(3); b = 1360.2(5); c = 1326.3(6)pm; α = 117.85(4); ß = 111.05(3); γ = 72.09(3)°; Z = 2. Due to ring folding at the P1? P2 axis of 149.1°, the molecule shows pseudosymmetry Cs. Characteristic averaged bond lengths and angles obtained at an Rw-value of 0.030, are: P? C(endocyclic) 188 and 191; P? CH3 184; C? S 183; S? Si 216 pm; C? P? CH3 105; P? C? S 113; S? C? S 114; C? S? Si 108; P? C? P 90 and C? P? C 86°. 相似文献
13.
Alessandra LattanziLiliana R. Orelli Patrizia BaroneAntonio Massa Patrizia IanneceArrigo Scettri 《Tetrahedron letters》2003,44(7):1333-1337
A mild and practical procedure of Horner-Wadsworth-Emmons olefination promoted by lithium hydroxide and α-cyano phosphonates has been set up for the synthesis of α,β-unsaturated nitriles. The reaction conditions are tolerated by functionalized ketones and the exclusive formation of E-γ-hydroxy α,β-unsaturated nitriles has been observed. 相似文献
14.
Acyl- and Alkylidenephosphines. XXVII. Molecular and Crystal Structure of Methyl-[(N-phenyl, N-trimethylsilyl)thiocarbamoyl]trimethylsilylphosphine . Methyl[(N-phenyl, N-trimethylsilyl)thiocarbamoyl]trimethylsilylphosphine 1a formed via an addition of methylbis(trimethylsilyl)phosphine to phenyl isothiocyanate [1], crystallizes in the monoclinic centrosymmetric space group P21/n with following dimensions of the unit cell determined at a temperature of measurement of ?80±3°C: a=1041.2(4);b=1706.9(12);c=1001.1(6)pm; β=106.41(4)°; Z = 4. An X-ray structure determination (Rw = 0.039) confirms the constitution of the compound as already derived from its nmr spectra. One trimethylsilyl group is bound to the phosphorus atom, whereas the other is connected with the sp2-hybridized nitrogen atom. Characteristic rounded bond lenghts and angles are: P? Si 231, P? CH3 184, P? C(S) 187, C?S 167, N? C(S) 137, and N? Si 181 pm as well as P? C? S 122°, P? C? N 117°, and S? C? N 121°. 相似文献
15.
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17.
E. M. Telles J. C. S. Moraes A. Scalabrin D. Pereira G. Carelli C. A. Massa A. Moretti F. Strumia 《International Journal of Infrared and Millimeter Waves》1995,16(12):2233-2248
We used a Stark-Optoacoustic cell and hybrid waveguide resonators to perform an Infrared and Far Infrared Stark Spectroscopy study on some transitions of13CD3OH. Different behaviours of the transitions in the presence of a d.c. electric field were observed. The Stark splittings of six FIR laser lines ranging from 34 to 136 MHz/kVcm–1 were determined. The analysis of the behaviour of the IR and FIR transitions in the presence of the external electric fields gives important and exclusive information on the levels involved in the transitions.Work Supported by FAPESP, CNPq, FAEP - Brazil, and CNR - Italy. 相似文献
18.
19.
Extended Gaussian orbital basis set calculations have been carried out on an assumed staggered and eclipsed classical geometrical configuration of C2H. The best total energies obtained for these geometries were ?78.170692 a.u. and ?78.170674 a.u. respectively, corresponding to a barrier to internal rotation of 1.8 × 10?5 a.u. or 11 kcal/mole. An analysis of the charge density matrix indicates that charge is distributed in these molecules in a manner consistent with the concept of hyperconjugation. 相似文献
20.
The Crystal Structure of Na2NiAlF7 — a Contribution to the Problem of the True Space Group of Orthorhombic Weberites The X-ray single crystal structure determination of the orthorhombic weberite Na2NiAlF7 (a = 707.4(2), b = 1003.8(2), c = 731.5(1) pm; Z = 4) was performed in space group Imma, after all reflections hk0 with h(k) = 2n + 1 could be eliminated, as they proved simulated by Renninger effect and/or λ/2 reflections. The alternative space groups Imm2 resp. I212121 of former weberite structure determinations thus became obsolete. The refinement using 880 independent reflections ended at wR = 0.0232. The resulting average distances within the framework of octahedra are Ni? F = 197.3, Al? F = 180.4 pm. 相似文献