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Reaction Behaviour of Copper(I) and Copper(II) Salts Towards P(C6H4CH2NMe2‐2)3 ‐ the Solid‐State Structures of {[P(C6H4CH2NMe2‐2)3]CuOClO3}ClO4, {[P(C6H4CH2NMe2‐2)3]Cu}ClO4, [P(C6H4CH2NMe2‐2)3]CuONO2 and [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐‐2)]CuONO2 The reaction behaviour of P(C6H4CH2NMe2‐2)3 ( 1 ) towards different copper(II) and copper(I) salts of the type CuX2 ( 2a : X = BF4, 2b : X = PF6, 2c : X = ClO4, 2d : X = NO3, 2e : X = Cl, 2f : X = Br, 13 : X = O2CMe) and CuX ( 5a : X = ClO4, 5b : X = NO3, 5c : X = Cl, 5d : X = Br) is discussed. Depending on X, the transition metal complexes [P(C6H4CH2NMe2‐2)3Cu]X2 ( 3a : X = BF4, 3b : X = PF6), {[P(C6H4CH2NMe2‐2)3]CuX}X ( 4 : X = ClO4, 11a : X = Cl, 11b : X = Br, 14 : X = O2CMe), {[P(C6H4CH2NMe2‐2)3]Cu}ClO4 ( 6 ), [P(C6H4CH2NMe2‐2)3]CuX ( 7a : X = Cl, 7b : X = Br, 10 : X = ONO2), [P(C6H4CH2NMe2‐2)2(C6H4CH2NMe2H+NO3‐‐2)]CuONO2 ( 9 ) and [P(C6H4CH2NMe2‐2)3]CuCl}CuCl2 ( 12 ) are accessible. While in 3a , 3b and 6 the phosphane 1 preferentially acts as tetrapodale ligand, in all other species only the phosphorus atom and two of the three C6H4CH2NMe2 side‐arms are datively‐bound to the appropriate copper ion. In solution a dynamic behaviour of the latter species is observed. Due to the coordination ability of X in 3a , 3b and 6 non‐coordinating anions X‐ are present. However, in 4 one of the two perchlorate ions forms a dative oxygen‐copper bond and the second perchlorate ion acts as counter ion to {[P(C6H4CH2NMe2‐2)3]CuOClO3}+. In 7 , 9 and 10 the fragments X (X = Cl, Br, ONO2) form a σ‐bond with the copper(I) ion. The acetate moiety in 14 acts as chelating ligand as it could be shown by IR‐spectroscopic studies. All newly synthesised cationic and neutral copper(I) and copper(II) complexes are representing stable species. Redox processes are involved in the formation of 9 and 12 by reacting 1 with 2 . The solid‐state structures of 4 , 6 , 9 and 10 are reported. In the latter complexes the copper(II) ( 4 ) or copper(I) ion ( 6 , 9 , 10 ) possesses the coordination number 4. This is achieved by the formation of a phosphorus‐ and two nitrogen‐copper‐ ( 4 , 9 , 10 ) or three ( 6 ) nitrogen‐copper dative bonds and a coordinating ( 4 ) or σ‐binding ( 9 , 10 ) ligand X. In 6 all three nitrogen and the phosphorus atoms are coordinatively bound to copper, while X acts as non‐coordinating counter‐ion. Based on this, the respective copper ion occupies a distorted tetrahedral coordination sphere. While in 4 and 10 a free, neutral Me2NCH2 side‐arm is present, which rapidly exchanges in solution with the coordinatively‐bound Me2NCH2 fragments, this unit is protonated in 10 . NO3‐ acts as counter ion to the CH2NMe2H+ moiety. In all structural characterized complexes 6‐membered boat‐like CuPNC3 cycles are present. 相似文献
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From the reaction of 1‐HOCPh2‐2‐NMe2C6H4 ( 1 ), 1‐HOC(C6H11)2‐2‐NMe2C6H4 ( 2 ) and 1‐HOCPh2CH2‐2‐NMe2C6H4 ( 3 ) with n‐BuLi in diethyl ether, the solvent‐free chelated dimethylamino lithium alkoxides [1‐LiOCPh2‐2‐NMe2C6H4]2 ( 4 ), [1‐LiOC(C6H11)2‐2‐NMe2C6H4]2 ( 5 ) and [1‐LiOCPh2CH2‐2‐NMe2C6H4]2 ( 6 ) were obtained. The lithium alkoxides 4 – 6 were characterized by 1H, 7Li, and 13C NMR spectroscopy. Crystal structure determinations of 5 and 6 were carried out. Compounds 5 and 6 are examples of structurally characterized solvent‐free chelated dimethylamino lithium alkoxides and 6 is a rare example of this type containing a seven‐membered ring. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
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The neutral thorium complex Th(NCSe)4(OP(NMe2)3)4 and homoleptic octa(isoselenocyanato)uranate anion U(NCSe)84– in (Pr4N)4U(NCSe)8·2CFCl3 ( 1 ) were synthesised and structurally characterised. (Pr4N)4U(NCSe)8·2CFCl3 contains the UIV anion U(NCSe)84– and was characterised using IR spectroscopy and single‐crystal X‐ray diffraction. Th(NCSe)4(OP(N(CH3)2)3)4·0.5CH3CN·0.5H2O ( 2 ) was characterised using IR and Raman spectroscopy, as well as 31P{1H}, 15N{1H}, 14N{1H}, 13C{1H}, 1H and 77Se NMR spectroscopy and structurally characterised using single‐crystal X‐ray diffraction. The U(NCSe)84– anion and Th(NCSe)4(OP(N(CH3)2)3)4·0.5CH3CN·0.5H2O complex are the first structurally characterised actinide‐isoselenocyanates. The crystal structures shows an approximate square antiprismatic arrangement of the ligands around the actinide(IV) atoms. 相似文献
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Bipy, Phen, and P(C6H4CH2NMe2‐2)3 in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C6H4CH2NMe2‐2)3]AgOTf and [Ag(phen)2]OTf The reaction of [P(C6H4CH2NMe2‐2)3]AgX ( 1a , X = OTf; 1b , X = OClO3) with equimolar amounts of LcapL ( 2a , LcapL = 2, 2′‐bipyridine, bipy; 2b , LcapL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , LcapL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C6H4CH2NMe2‐2)3]Ag(LcapL)}+X— (LcapL = bipy: 3a , X = OTf; 3b , X = ClO4; LcapL = bipy′: 3c , X = OTf; 3d , X = ClO4; LcapL = phen: 3e , X = OTf; 3f , X = ClO4) in which the building blocks LcapL and P(C6H4CH2NMe2‐2)3 act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me2NCH2 built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C6H4CH2NMe2‐2)3 ( 5 ) along with [Ag(phen)2]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P21/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)Å3 and Z = 4 with 8132 observed unique reflections (R1 = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)Å3 and Z = 4 with 6209 observed unique reflections (R1 = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH2C2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion. 相似文献
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The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is [(3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. 相似文献
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Treatment of GaCl3 with one equiv of Li[NC4H3(CH2NMe2)‐2] (n = 1, 2, 3) in diethyl ether at ?78 °C yields GaCl3‐n[NC4H3(CH2NMe2)‐2]n (n = 1, 1 ; n = 2, 2 ; n = 3, 3 ). Compound 1 reacts with two equiv of RLi to afford GaR2[NC4H3(CH2NMe2)‐2] ( 4a, R=Me; 4b, R=Bu ) via transmetallation. Reacting 2 with one equiv of RLi in diethyl ether, 3 and 4 are formed via ligand redistribution. Variable temperature 1H NMR spectroscopic experiments reveal that the five‐coordinate gallium compound 3 is fluxional and results in a coalescence temperature at 5 °C, at which ΔG≠ is calculated at ca. 10.4 Kcal/mole. All the new compounds have been characterized by 1H and 13C NMR spectroscopy and the structures of compounds 3 and 4a have also been determined by X‐ray crystallography. 相似文献
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M. Leschke M. Melter C. Weber G. Rheinwald H. Lang A. Driess G. Huttner 《无机化学与普通化学杂志》2001,627(6):1199-1203
Synthesis of Monomeric T‐Shaped Silver(I) Halide Complexes – Crystal Structure Analysis of [P(C6H4CH2NMe2‐2)3]AgBr Treatment of the tetrapodal phosphane P(C6H4CH2NMe2‐2)3 ( 1 ) with equimolar amounts of the silver(I) halides AgX ( 2 a : X = Cl, 2 b : X = Br) produces in tetrahydrofuran at 25 °C the monomeric silver(I) complexes [P(C6H4CH2NMe2‐2)3]AgX with planar coordination at the Ag atoms ( 3 a : X = Cl, 3 b : X = Br) in excellent yields. From complex 3 b a single X‐ray crystal structure analysis was carried out. Mononuclear 3 b crystallizes in the monoclinic space group P21/c with the cell parameters a = 14.504(6), b = 11.034(3), c = 17.604(5) Å, β = 102.86(4)°; V = 2746.6(16) Å3; Z = 4; 2953 observed unique reflections, R1 = 0.0805. Complex 3 b consists of monomeric sub‐units with a planar T‐shaped arrangement formed by the atoms Ag1, N1, P1 as well as Br1, whereby the P1–Ag1–Br1 array is almost linear orientated. 相似文献
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Weber L Meyer M Stammler HG Neumann B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(24):5401-5408
The reaction of the arylated Fischer carbene complexes [(CO)5M=C(OEt)Ar] (Ar=Ph; M = Cr, W; 2-MeC6H4; 2-MeOC6H; M = W) with the phosphaalkenes RP=C(NMe2), (R=tBu, SiMe3) afforded the novel phosphaalkene complexes [[RP=C(OEt)Ar]M(CO)5] in addition to the compounds [(RP=C(NMe2)2]M(CO)5]. Only in the case of the R = SiMe3 (E/Z) mixtures of the metathesis products were obtained. The bis(dimethylamino)methylene unit of the phosphaalkene precursor was incorporated in olefins of the type (Me2N)2C=C(OEt)(Ar). Treatment of [(CO)5W=C(OEt)(2-MeOC6H4)] with HP=C(NMe2)2 gave rise to the formation of an E/Z mixture of [[(Me2N)2CH-P=C(OEt)(2-MeOC6H4)]W(CO)5] the organophosphorus ligand of which formally results from a combination of the carbene ligand and the phosphanediyl [P-CH(NMe2)2]. The reactions reported here strongly depend on an inverse distribution of alpha-electron density in the phosphaalkene precursors (Pdelta Cdelta+), which renders these molecules powerfu] nucleophiles. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(42):13105-13109
The reaction of (C5Me5)2Th(CH3)2 with the phosphonium salts [CH3PPh3]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C5Me5)2Th[CHPPh3]X, rare terminal phosphorano‐stabilized carbenes with thorium. These complexes feature the shortest thorium–carbon bonds (≈2.30 Å) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C5Me5)2Th[κ2‐(C,C′)‐(CH2)(CH2)PPh2]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH3PPh3]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. 相似文献