[Co(g5‐Me5C5)(g3‐tBu2PPCH–CH3)] aus [Co(g5‐Me5C5)(g2‐C2H4)2] und tBu2P–P=P(Me)tBu2

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVII [1] [Co(g⁵‐Me₅C₅)(g³‐^tBu₂PPCH–CH₃)] from [Co(g⁵‐Me₅C₅)(g²‐C₂H₄)₂] and ^tBu₂P–P=P(Me)^tBu₂ [Co(η⁵‐Me₅C₅)(η³‐^tBu₂PPCH–CH₃)] 1 is formed in the reaction of [Co(η⁵‐Me₅C₅)(η²‐C₂H₄)₂] 2 with ^tBu₂P–P 4 (generated from ^tBu₂P–P=P(Me)^tBu₂ 3 ) by elimination of one C₂H₄ ligand and coupling of the phosphinophosphinidene with the second one. The structure of 1 is proven by ³¹P, ¹³C, ¹H NMR spectra and the X‐ray structure analysis. Within the ligand ^tBu₂P¹P²C¹H–CH₃ in 1 , the angle P1–P2–C1 amounts to 90°. The Co, P1, P2, C1 atoms in 1 look like a „butterfly”︁. The reaction of 2 with a mixture of ^tBu₂P–P=P(Me)^tBu₂ 3 and ^tBu–C?P 5 yields [Co(η⁵‐Me₅C₅){η⁴‐(^tBuCP)₂}] 6 and 1 . While 6 is spontaneously formed, 1 appears only after complete consumption of 5 .     

Chlorido(η5‐cyclopentadienyl)bis(dimethylamido)titanium, [TiCl(η5‐C5H5)(NMe2)2]

The title complex, [Ti(C₅H₅)(C₂H₆N)₂Cl], exhibits two nearly planar dimethylamide groups oriented approximately perpendicular to each other. The Ti→cyclopentadienyl centroid vector lies nearly in the plane of one of the dimethylamide groups. Long‐range contacts between Ti—Cl and cyclopentadienyl H—C groups give rise to geometric ordering in the extended solid.     

Synthesen und Charakteristika von Heterobimetallorganika des Siliciums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)]—

Syntheses and characteristics of the heterobimetalorganics of the silicon with the 2‐(dimethylaminomethyl)ferrocenyl ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)]^— The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, LiFcN, reacts with silicon(IV)‐chlorid, SiCl₄, under the formation of heterobimetallic silicon(IV) organyl [(FcN)₃SiCl] ( 1 ). The heterobimetallic organosilanol [(FcN)₃SiOH] ( 2 ) is formed at hydrolysis of 1 . A detailed characterization of the defined compounds 1 and 2 was carried out by NMR‐ rsp. mass‐spectrometry and by crystal X‐ray analysis of 2 .     

[(η5‐C5R5)TiCl2(η5‐C5H4SiMe2)]2O·nCH2Cl2

The first title metallocene, 1,3‐bis(dichlorotitanocene)‐1,1,3,3‐tetramethyldisiloxane dichloromethane solvate, [(η⁵‐C₅H₅)­TiCl₂­(η⁵‐C₅H₄­Si­Me₂)]₂O·­CH₂Cl₂, (I), crystallizes in space group P2₁/c. Compound (I) represents the first crystal structure of a bimetallic siloxy‐bridged titanocene. The geometric parameters of (I) are similar to those of the parent titanocene; however, the disiloxane substituents adopt an unexpected eclipsed conformation. The second title metallocene, 1,3‐bis­[(penta­methyl­cyclo­penta­dienyl)­(cyclo­penta­dien­yl)­titanium dichloride]‐1,1,3,3‐tetra­methyl­disiloxane, [(η⁵‐C₅‐Me₅)­TiCl₂­(η⁵‐C₅H₄­Si­Me₂)]₂O, (II), represents the second crystal structure of a bimetallic siloxy‐bridged titanocene and crystallizes in the space group P2₁/n. Compound (I) possesses non‐crystallographic twofold molecular symmetry and both metal centers adopt pseudo‐tetrahedral geometries. The geometric parameters of (II) are similar to those of the mixed titanocene Cp*CpTiCl₂ (Cp* = C₅Me₅) and the disiloxane substituents adopt a staggered conformation.     

Synthese und Kristallstruktur des heterobimetallischen Diorganozinndichlorids (FcN,N)2SnCl2 (FcN,N—: (η5‐C5H5)Fe{(η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}—)

Synthesis and Crystal Structure of the Heterobimetallic Diorganotindichloride (FcN, N)₂SnCl₂ (FcN, N^—: (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2}^—) The heterobimetallic title compound [(FcN, N)₂SnCl₂] ( 1 ) was obtained by the reaction of [LiFcN, N] with SnCl₄ in the molar ratio 1:1 in diethylether as a solvent. The two FcN, N^— ligands in 1 are bound to Sn through a C‐Sn σ‐bond; the amino N atoms of the side‐chain in FcN, N^— remain uncoordinated. The crystals contain monomeric molecules with a pseudo‐tetrahedral coordination at the Sn atom: Space group P2₁/c; Z = 4, lattice dimensions at —90 °C: a = 9.6425(2), b = 21.7974(6), c = 18.4365(4) Å, β = 100.809(2)°, R1_obs· = 0.051, wR2_obs· = 0.136.     

Nucleophilic Transfer Reactions of the [Si(C2F5)3]− Moiety

The tris(pentafluoroethyl)silanide anion is accessible by the deprotonation of Si(C₂F₅)₃H at low temperatures. Subsequent quenching of the resulting salt‐like compounds with suitable electrophiles, such as transition‐metal complexes or Group 14 element halides, leads to a plethora of novel tris(pentafluoroethyl)silane derivatives. This underlines the versatility of Li[Si(C₂F₅)₃] as a powerful nucleophilic transfer reagent.     

Darstellung,Eigenschaften und Molekülstrukturen von Heterobimetallorganika des vierwertigen Germaniums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)‐2]

Hydrolysereak‐Syntheses, Properties and Molecular Structures of the Heterobimetalorganics of the four‐valued Germanium with the 2‐(Dimethylaminomethyl)ferrocenyl Ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)‐2] The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, FcNLi, reacts with germanium(IV) chloride, GeCl₄, under the formation of heterobimetallic germanium(IV) organyls (FcN)_nGeCl_4‐n (n = 2 ( 1 ), 3 ( 2 )). The heterobimetallic organogermanol (FcN)₃GeOH ( 3 ) is formed at hydrolysis of 2 . A detailed characterization of the defined compounds 1 — 3 was carried out by single crystal X‐ray analyses, NMR‐ and mass‐spectrometry.     

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     

Isolation of New Disilanylene-bridged Bis（cyclopentadienyl）tetracarbonyldiiron Complexes and Molecular Structure of [η^5, η^5-C5H4SiMe（SiMePh2）C5H4]Fe2（CO）2（μ-CO）2

1,2-Diphenyl-1,2-dimethyldisilanylene-bridged bis-cyclopentadienyl complex[η~5,η~5-C_5H_4PhMeSiSiMePh-C_5H_4]Fe_2(CO)_2(μ-CO)_2(1)was synthesized by a modified procedure,from which the trans-isomer 1b that was pre-viously difficult to obtain has been isolated for the first time.More interestingly,two new regio-isomers[η~5,η~5C_5H_4SiMe(SiMePh_2)C_5H_4]Fe_2(CO)_2(μ-CO)_2(2)and [η~5,η~5-C_5H_4Me_2SiSiPh_2C_5H_4]Fe_2(CO)_2(μ-CO)_2(3)were occa-sionally obtained during above process,the novel structures of which opened up new options for further study ofthis type of Si—Si bond-containing transition metal complexes.The molecular structure of 2 has been determinedby the X-ray diffraction method.     

Heteroleptic [n]Chromoarenophanes: ansa Complexes Derived from [Cr(η5‐C5H5)(η6‐C6H6)]

The synthesis of ansa complexes has been studied intensively owing to their importance as homogeneous catalysts and as precursors of metal‐containing polymers. However, paramagnetic non‐metallocene derivatives are rare and have been limited to examples with vanadium and titanium. Herein, we report an efficient procedure for the selective dilithiation of paramagnetic sandwich complex [Cr(η⁵‐C₅H₅)(η⁶‐C₆H₆)], which allows the preparation of a series of [n]chromoarenophanes (n=1, 2, 3) that feature silicon, germanium, and tin atoms at the bridging positions. The electronic and structural properties of these complexes were probed by X‐ray diffraction analysis, cyclic voltammetry, and by UV/Vis and EPR spectroscopy. The spectroscopic parameters for the strained and less strained complexes (i.e., with multiple‐atom linkers) indicate that the unpaired electron resides primarily in a d orbital on chromium(I); this result was also supported by density functional theory (DFT) calculations. We did not observe a correlation between the experimental UV/Vis and EPR data and the degree of molecular distortion in these ansa complexes. The treatment of tin‐bridged complex [Cr(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] results in the non‐regioselective insertion of the low‐valent Pt⁰ fragment into the C_ipso? Sn bonds in both the five‐ and six‐membered rings, thereby furnishing a bimetallic complex. This observed reactivity suggests that ansa complexes of this type are promising starting materials for the synthesis of bimetallic complexes in general and also underline their potential to undergo ring‐opening processes to yield new metal‐containing polymers.