[C5H5Fe(CO)2]LnCl2·nTHF和[C5H5Fe(CO)2][C5H4(SiMe3)]LnCl·nTHF双核配合物的合成

合成了稀土铁双核配合物:(C₅H₅Fe(CO)₂)LnCl₂·nTHF(Ln=Nd,Sm,Gd;n=1,2)和(C₅H₅Fe(CO)₂)(C₅H₄(SiMe₃))·LnCl·nTHF(Ln=Nd,Sm,Gd;n=0,1,2)。元素分析,热分析,红外光谱和质谱分析确认了这两种配合物。红外光谱数据表明铁与稀土原子是以羰基桥连接。晶体结构分析表明((C₅H₅Fe(CO)₂)Na·4THF是(C₅H₅Fe(CO)₂)LnCl₂·nTHF合成的中间体。     

Zur Polyreaktion von Äthylen mit dem löslichen Ziegler-Natta-Katalysator (C5H5)2Ti(C2H5)Cl/Al(C2H5)Cl2

Ohne Zusammenfassung     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Zur disproportionierung der phenylfluorphosphane (C6H5)2PF und (C6H5)PF2

Ph₂P-PF₂Ph₂ has been identified by means ¹⁹F- and ³¹P- NMR spectroscopy as an intermediate product of the disproportionation of Ph₂PF. The disproportionation is catalyzed by acids. The reaction mechanism is discussed. PhPF₂ disproportionates faster in solution in acetonitrile than neat, forming (PhP)₆, instead of (PhP)₅.     

Syntheses and crystal structures of [(C6H5CH2C5H4)2GdCl.THF]2 and (C6H5CH2C5H4)2ErCl.THF

[(C₆H₅CH₂C₅H₄)₂GdCl.THF]₂ (1) and (C₆H₅CH₂C₅H₄)₂ErCl.THF (2) were prepared by the reaction of LnCl₃ (Ln? Gd, Er) with benzylcyclopentadienyl sodium in THF and characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR, MS and thermal gravimetry. The crystal structures of both compounds were determined. Complex 1 is dimeric and its structure belongs to the monoclinic, P2₁/c space group with a=1.1432(2), b=1.2978(2), c=1.7604(3) nm, β=108.75(2), V=2.4732(9) nm³, Z=2(four monomers), D_c“1.54 g.cm^?3. R=0.0342 and R_w“0.0362. Complex 2 is monomer and its structure belongs to the orthorhombic, P2₁2₁2₁ space group with a=0.8645(2), b=1.1394(3), c=2.5289(4) nm, V=2.4919(9) nm³, Z=4, D_c“1.56 g.cm^?3. R=0.0514, R_w“0.0529. The determination of the crystal structure shows that in complex 1 the benzyl groups on the cyclopentadienyls coordinated to Gd³⁺ are located in the opposite direction (139°); in complex 2 the benzyl groups on the cyclopentadienyls coordinated to Er³⁺ are located in the same direction (6.5°).     

Syntheses and Anti—inflammatory Actiobn of （η—C5H5）2Ti （Cin）2 and （η—C5H5）2Ti（Tzea）2

Two new Complexes(Cp)2Ti(Cin)2and (CP2)Ti(Tzea)2(CP=Cyclopentadienyl η^5-C5H5)have been synthesized in THF by the reaction of HCin(Cincofen,2-phenylquinoline-4-carboxylic acid)or HTzea(5-phenyltetrazolyl-2-ethanoic acid)with(Cp)2TiCl2,and characterized by elemental analyses,IR,1H NMR and 13C NMR,UV spectra,molar conductivity,TGDTA.In the complexes the carboxyl groups are coordinated to Ti(IV)in a monodentate manner,The inhibitory actions of the complexes on mice ear tumefaction caused by croton oil and the rat foot granulation growth produced by cotton wool are higher than those of the corresponding ligands HCin,HTzea and [(Cp)2TiCl2],while their toxicities are lower than those of the free ligands.ηη     

混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构研究

本文用电化学方法和X射线单晶结构分析, 研究了混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构, 由循环伏安结果, 分别讨论了簇合物中(C5H5FeC5H4和C2O2中心的成键性质, X射线单晶结构分析表明: 晶体属单斜晶系, 空间群为P21, 晶胞参数a=11.845(6), b=8.155(6), c=24.031(6)A, β=90.88°,晶胞中分子数Z=4, 密度Do=1.637g.cm^-^2, 分析了(C5H5FeC5H4C2Ph)Co2(CO)6的结构特点, 并从成键角度讨论了(RC2R^1)Co(CO)6类簇合物的结构随RC2R^1不同而变化的规律。     

Syntheses and structures of Mg(C5H5BMe)2, Mg(3,5-Me2C5H3BNMe2)2, the 2,2'-bipyridine adduct Mg(C5H5BMe)2(bipy), and the N-bonded aminoboratabenzene species Mg(3,5-Me2C5H3BNMe2)2(THF)2

The donor-free magnesocene analogues bis(1-methylboratabenzene)magnesium (1) and bis[3,5-dimethyl-1- (dimethylamino)boratabenzene]magnesium (2) are synthesized in good yields by the reactions of dimethylmagnesium with (trimethylstannyl)dihydroborinine precursors 3 and 4. In the crystalline state, both 1 and 2 possess sandwich structures with eta 6-coordinated boratabenzene ligands and display crystallographic centrosymmetry. Compound 1 reacts with the nitrogen donor 2,2'-bipyridine to give the Lewis base adduct (1)(bipy) (identical to 5). In the crystal structure of 5, one boratabenzene ligand is eta 6-bonded to the central metal while the other ligand adopts an eta 1-bonding mode. Crystallization of compound 2 from THF produces the solvate (2)(THF)2 (identical to 6), which exhibits a distorted tetrahedral N2O2 coordination environment around the magnesium atom. The average Mg-N bond distance is 2.141(3) A, and the N-Mg-N angle is 148.0(1) degrees. The observation of an aminoboratabenzene that is solely sigma-bonded to a metal is without precedent.