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111.
Synthesis, Structure, and Photolysis of Isocyanato Complexes of Rhenium The ReIII isocyanato complex Re(NCO)3(PMe2Ph)3 yields from the reaction of ReCl3(PMe2Ph)3 with an excess of NaOCN in EtOH. It crystallizes in the triclinic space group P 1 with a = 991.8(6), b = 1180.7(6), c = 1348.8(5) pm, α = 89.85(1)°, β = 94.12(1), γ = 111.56(1)°, Z = 2. In the mononuclear complex with an octahedral coordination of the Re atoms the phosphine and isocyanato ligands exhibit a meridional arrangement. By using a deficient amount of NaOCN the mono isocyanato complex Re(NCO)Cl2(PMe2Ph)3 is formed, and part of the educt is transformed to its isomer [(Me2PhP)3Re(μ-Cl)3Re(PMe2Ph)3]Cl3. The mono isocyanato complex forms monoclinic crystals with the space group P21/n and a = 1467.5(7), b = 1310.6(7), c = 1603.2(8) pm, β = 112.08(1)°, Z = 4. The isocyanato ligand is in trans position to a Cl atom, and the phosphine ligands are coordinated in a meridional arrangement. [(Me2PhP)3Re(μ-Cl)3Re(PMe2Ph)3]Cl3 · 2 EtOH crystallizes in the hexagonal space group P63/m with a = 1332.6(2), c = 2300.1(7) pm, Z = 2. The dinuclear complex cation occupies with its center a special position with the symmetry C3h. Photolysis of Re(NCO)Cl2(PMe2Ph)3 results in the cleavage of the isocyanato ligand with release of CO and formation of the nitrido complex ReNCl2(PMe2Ph)3. The reaction of ReNCl2(PMe2Ph)3 with NaOCN affords the complex ReN(NCO)2(PMe2Ph)3. It crystallizes in the space group P21/n with a = 943.0(3), b = 2635.2(4), c = 1212.6(5) pm, β = 109.88(1)°, Z = 4. In this nitrido complex, like in the educt, the phosphine ligands form a meridional arrangement. The nitrido ligand is in trans position to an isocyanato group. The distance Re≡N is 165.9(6) pm. 相似文献
112.
Amido Ligands for the Synthesis of Polynuclear Lanthanoid Complexes By 1 : 1 reaction of LnBr3 with NaNHPh in THF the Rare-Earth Complexes [Ln2Br4(μ2-NHPh)2(thf)5] (Ln = Sm ( 1 ), Ln = Gd ( 2 )) with two bridging anilido ligands are obtained. In the system LnBr3/NaNHPh/(Me2SiO)3 the tetranuclear compounds [Ln4(μ4-O)(NHPh)3(OSiMe2NPh)6Na5(thf)7] · THF (Ln = Gd ( 3 ), Ln = Yb ( 4 )) can be built up. They have a central μ4-oxygene atom in the Ln4-tetrahedron. It has an oxa-dimethylsilyl-N-phenylamido ligand over all edges and an anilido ligand on three vertexes. By this reaction small amount of [Na4(thf)6Yb2(OSiMe2NPhSiMe2O)2(OSiMe2NPh)2(NHPh)2] ( 5 ) with a O- and N-bridged Yb–Na polyhedron and N-phenyl-bis(dimethylsilanolato)-ligands coordinating μ2-η2 with its oxygen atoms are obtained. Reaction of Lanthanideshalides with LiNHtBu leads to dimeric complexes. The formation of bridging oxasilylamido ligands is also observed. The compound [Li2Ln(OSiMe2NtBu)2(HNtBu)(thf)]2 (Ln=Sm ( 6 ), Gd ( 7 ) and Yb ( 8 )) contains now an O- and N-bridged Ln–Li polyhedron. (Crystal Data of 1–8 see ‘‘Inhaltsverzeichnis”︁”︁). 相似文献
113.
N,N -Dimethylcarbamato Complexes of Copper and Zinc Reactions of the 1 : 1 adduct of dimethylamine and carbon dioxide (dimcarb) with metallic copper and zinc, respectively, are reported. Dimcarb gives with copper in the presence of oxygen the N,N-dimethylcarbamato copper(II) complex [Cu(O2CNMe2)2(HNMe2)2] ( 1 ). Zinc spontaneously dissolves in a dimcarb-acetonitrile mixture under generation of hydrogen and giving (H2NMe2)[Zn2(O2CNMe2)5] · MeCN ( 3 ). The rate of this reaction is strongly depending on the purity of the metal, high purity zinc doesn't react. But 3 can be prepared from it by electrosynthesis. The crystal structures of 1 and 3 were determined by X-ray analysis. In 1 the copper atom has a distorted octahedral coordination sphere in which the two carbamate ligands are chelating. In the homoleptic complex anion of 3 two zinc atoms are bridged by three carbamate ligands whereas the other two carbamate ligands are coordinated monodentately. 相似文献
114.
[ScCl2{N(SiMe3)2}(THF)2] – a Precursor for the Synthesis of Scandium Nitride [ScCl2{N(SiMe3)2}(THF)2] ( 1 ) has been prepared by the reaction of [ScCl3(THF)3] with the trisamide Sc[N(SiMe3)2]3 in tetrahydrofurane solution forming colourless moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P 1, Z = 2, lattice dimensions at –50 °C: a = 841.4(1), b = 924.2(1), c = 1550.0(1) pm, α = 90.046(7)°, β = 95.671(9)°, γ = 106.066(6)°, R1 = 0.0329. In the molecular structure of 1 the scandium atom has a distorted trigonal‐bipyramidal coordination with the THF molecules in apical positions. At 400 °C 1 is converted into scandium nitride, ScN, by stepwise leaving of THF and ClSiMe3. 相似文献
115.
Syntheses and Crystal Structures of the Nitrido‐chloro‐molybdates [Mg(THF)4{NMoCl4(THF)}2] · 4 CH2Cl2 and [Li(12‐Crown‐4)(NMoCl4)]2 · 2 CH2Cl2 Both the title compounds as well as [Li(12‐crown‐4)2]+MoNCl4– were made from MoNCl3 and the chlorides MgCl2 and LiCl, respectively, in dichloromethane suspensions in the presence of tetrahydrofuran and 12‐crown‐4, respectively. They form orange‐red moisture‐sensitive crystals, which were characterized by their IR spectra and partly by crystal structure analyses. [Mg(THF)4{NMoCl4(THF)}2] · 4 CH2Cl2 ( 1 ): space group C2/m, Z = 2, lattice dimensions at –50 °C: a = 1736.6(1), b = 1194.8(1), c = 1293.5(2) pm; β = 90.87(1)°; R1 = 0.037. In 1 the magnesium ion is coordinated octahedrally by the oxygen atoms of the four THF molecules and in trans‐position by the nitrogen atoms of the two [N≡MoCl4(THF)]– ions. [Li(12‐crown‐4)(NMoCl4)]2 · 2 CH2Cl2 ( 2 ): space group P 1, Z = 1, lattice dimensions at –70 °C: a = 930.4(1), b = 957.9(1), c = 1264.6(1) pm; α = 68.91(1)°, β = 81.38(1)°, γ = 63.84(1)°; R1 = 0.0643. 2 forms a centrosymmetric ion ensemble in the dimeric cation of which, i. e. [Li(12‐crown‐4)]22+, the lithium ions on the one hand are connected to the four oxygen atoms each of the crown ether molecules in a way not yet known; and in addition, each of the lithium ions enters into a intermolecular Li–O bond with neighboring crown ether molecules under formation of a Li2O2 four‐membered ring. The two N≡MoCl4– counterions are loosely coordinated to one oxygen atom each of the crown ether molecules with Mo–O distances of 320.2 pm. 相似文献
116.
Paul‐Michael Pellny Vladimir V. Burlakov Wolfgang Baumann Anke Spannenberg Uwe Rosenthal 《无机化学与普通化学杂志》1999,625(6):910-918
The reactions of the bis(trimethylsilyl)acetylene permethylmetallocene complexes CpM(η2‐Me3SiC2SiMe3) (M = Ti ( 1 ), M = Zr ( 2 )) with H2O and CO2 were studied and compared to those of the corresponding metallocene complexes Cp2M(L)(η2‐Me3SiC2SiMe3) (M = Ti ( 3 ), L = – ; M = Zr, L = THF ( 4 )) to understand the influence of the ligands Cp(η5‐C5H5) and Cp*(η5‐C5Me5) as well as the metals titanium and zirconium on the reaction pathways and the obtained products. In the reaction of the permethyltitanocene complex 1 with water the dihydroxy complex CpTi(OH)2 ( 5 ) was formed. This product differs from the well‐known titanoxane Cp2TiOTiCp2 which was obtained by the reaction of the corresponding titanocene complex 3 with water. The reaction of the permethylzirconocene complex 2 with water gives the mononuclear alkenyl zirconocene hydroxide 6 . An analogous product was assumed as the first step in the reaction of the corresponding zirconocene complex 4 with water which ends up in a dinuclear zirconoxane. In the conversion of the permethylzirconocene complex 2 with carbon dioxide the mononuclear insertion product 7 was formed by coupling of carbon dioxide and the acetylene. In contrast, the corresponding zirconocene complex 4 affords, by an analogous reaction, a dinuclear complex. In additional experiments the known complex CpZr(η2‐PhC2SiMe3) ( 8 ) was prepared, starting from CpZrCl2 and Mg in the presence of PhC≡CSiMe3. This complex reacts with carbon dioxide resulting in a mixture of the regioisomeric zirconafuranones 9 a and 9 b . From these in the complex 9 a , having the SiMe3 group in β‐position to the metal, the Zr–C bond was quickly hydrolyzed by water to give the complex CpZr(OH)OC(=O)–C(SiMe3)=CHPh ( 10 a ) compared to complex ( 9 b ) which gives slowly the complex CpZr(OH)OC(=O)–CPh=CH(SiMe3) ( 10 b ). 相似文献
117.
Crystal Structures of the Terpyridine Complexes [Cd(terpy)Cl2], [Cu(terpy)(CN)Cl], and [Cu(terpy)][Cu(CN)3] · H2O By reaction of cadmium chloride with 2,2′ : 6′,2″-terpyridine (“terpy”) in water/acetone crystals of [Cd(terpy)Cl2] ( 1) were formed. The compound crystallizes monoclinic, space group P21/c, a = 1111.70(10), b = 823.10(7), c = 1643.00(14) pm, β = 93.913(1)°, Z = 4. Starting from mixtures of different molar ratios of copper(II) chloride, terpyridine, and KCN in water/methanole, two complexes of different composition were obtained. At the molar ratio of 1 : 1 : 2 a copper(II) coordination compound with both halide and pseudohalide ligands, [Cu(terpy)(CN)Cl] ( 2 ), was formed which also crystallizes monoclinic, P21/c, a = 1065.6(3), b = 824.6(2), c = 1644.5(7) pm, β = 98.214(3)°, Z = 4. At a molar ratio of 1 : 1 : 10 a partial reduction of copper(II) occured with formation of a mixed valency compound [Cu(terpy)][Cu(CN)3] · H2O ( 3 ) which crystallizes in the hexagonal space group P6522, with a = b = 800.29(1), c = 4771.05(7) pm, Z = 6. Compounds 1 and 2 are structurally similar, the coordination of the metal atoms is square pyramidal. Networks are formed by hydrogen bridges. In 3 the copper(II) ions show a distorted square planar coordination by the three N atoms of the terpy ligand and one N atom of a bridging CN– group, the copper(I) atoms, however, show trigonal planar coordination by three CN– ligands to which the water molecules are bonded by hydrogen bridges. Thus helical chains are formed which stretch in the direction of the screw axes. The EPR spectrum of 3 was measured. 相似文献
118.
S. Anfang J. Grebe M. Mhlen B. Neumüller N. Faza W. Massa J. Magull K. Dehnicke 《无机化学与普通化学杂志》1999,625(8):1395-1400
Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [AlCl2(NPEt3)]2, [GaI2(NPEt3)]2, and [GaI2(NPPh3)]2 [AlCl2(NPEt3)]2 ( 1 ) is made according to the known method by reaction of aluminium trichloride with the silylated phosphaneimine Me3SiNPEt3 in acetonitrile; it is isolated as colourless, moisture sensitive crystals. The phosphoraneiminato complexes [GaI2(NPEt3)]2 ( 2 ) and [GaI2(NPPh3)]2 ( 3 ), on the other hand, are obtained by redox reactions as pale yellow crystals; ( 2 ) of “gallium(I) iodide” with Me3SiNPEt3 in toluene and ( 3 ) of gallium with N-iodine triphenylphosphaneimine, INPPh3, in tetrahydrofuran. 1 and 3 are characterized spectroscopically and by crystal structure determinations; 2 is characterized only crystallographically. 1 : Space group Pbca, Z = 4; lattice dimensions at –70 °C: a = 1232.6(2), b = 1341.1(2), c = 1393.4(3) pm, R1 = 0.0315. 1 forms centrosymmetric molecules in which the Al atoms are linked via Al–N bonds of the two (NPEt3–) groups; with 185.0 and 184.4 pm these bonds are of almost the same lengths. 2 : Space group Pbca, Z = 4; lattice dimensions at –80 °C: a = 1380.0(1), b = 1311.0(1), c = 1429.1(1) pm, R1 = 0.0273. 2 crystallizes isotypically with 1 . The gallium atoms of the centrosymmetric Ga2N2 four-membered ring are connected with Ga–N distances of equal length (190.9 pm). 3 · THF: Space group P212121, Z = 2; lattice dimensions at –140 °C: a = 1494.6(1), b = 1536.3(1), c = 974.6(1) pm, R1 = 0.0382. 3 forms dimeric molecules in which the gallium atoms are linked via the N atoms of the (NPPh3–) groups to form a non-planar Ga2N2 four-membered ring of C2 symmetry with Ga–N bonds of equal lengths – within standard deviations – of 194.7 pm. The phosphoraneiminato groups are arranged in a synperiplanar way. 相似文献
119.
We report expanded porphyrins with pyridine rings and two neighboring carbonyl groups, which allow NiII ions to coordinate to the tripyrrinone‐type NNNO coordination structure with Ni?O bonds. The selectivity of tripyrrinone is superior to other pyrrolic or pyridinic cavities of expanded porphyrins. Introduction of α‐carbonyl pyridine next to the tripyrrolic conjugated structure is a powerful strategy for regioselective metalation of flexible expanded porphyrinoids. 相似文献
120.
由糠醛与水杨酰肼反应合成糠醛水杨酰腙席夫碱,然后再将其分别与过渡金属锌(Ⅱ)和铅(Ⅱ)作用合成两种新型的酰腙席夫碱配合物,并通过元素分析、紫外光谱、红外光谱等方法对所制备配合物进行表征。 相似文献