Synthesis and Crystal Structure of [ Cp* Ru(η6- C6H5B Ph3)]

The title complex [Cp*Ru(η6-C6H5BPh3)] has been synthesized by the reaction of [Cp*Ru(H2O)(NBD)]BF4 with H2 and NaBPh4, and its crystal structure was determined by singlecrystal X-ray diffraction analysis. It crystallizes in triclinic, space group P(1) with a = 11.0610(10), b = 11.2317(10), c = 12.3633(11) (A), α = 81.419(2), β = 67.8370(10), γ = 88.370(2)°, V= 1405.9(2) (A)3,Z= 2, C34H35BRu, Mr= 555.50, Dc = 1.312 g/cm3, F(000) = 576 and μ(MoKa) = 0.577 mm-1. The final R and wR are 0.0559 and 0.1483, respectively for 4365 observed reflections with I ＞ 2σ(Ⅰ). In the title complex, the four phenyl rings bonded to the B atom are deposited in a tetrahedral geometry,and one of the phenyl rings is η6-bonded to ruthenium.     

Study on Nucleophilic Additions to endo-tricyclo[5.2.1.0~(2,6)]deca-2(6),8-dien-3-one and an Unusual Payne Rearrangement of α,β-Epoxy Tricyclodecenone

The facial selectivity of nucelophilic additions to endo-tricyclo [5.2.1.02,6] deca-2(6),8-dien-3-one 1 demonstrates a high preference for exo-facial attack to the enone moiety1. We were interested in whether it would be possible to accomplish three-ring annulation to tricyclodecenone 1 by cyclopropanation or epoxidation. Three-ring annulation would lead to an increase in total ring strain as compared with the starting enone, not as previous nucleophilic addition reactions which release strain…     

Kinetics of η6→η5 isomerization of (η6-fluorenyl)(η5-cyclopentadienyl)iron

The kinetics of the reversible isomerization of the zwitterionic complex [(⁶-C₁₃H₉)Fe(⁵-C₅H₅)] (1) into dibenzoferrocene (2) was studied by electronic spectroscopy in the temperature range from 70 to 103 °C. The activation parameters of the reaction 1 2 were determined, E _a = 22.5 kcal mol^–1.     

Synthesis and Crystal Structure of [CpRu(η5-C5H5)(dppc)Cl][PF6]

The title complex [Ru(η5-C5H5)(dppc)Cl][PF6] has been synthesized by the reaction of [Ru(η5-C5H5)(PPh3)2Cl] with [dppc][PF6] (1,1'-bis(diphenylphosphino)cobaltocenium hexaflurophospate) in CH2Cl2, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 15.754(8), b =13.704(7), c=19.120(10) (A),β=106.148(9)°, V=3965(4) (A)3, Z=4, C40H35Cl3CoF6P3Ru, Mr=988.94, Dc=1.657 g/cm3, F(000) = 1984 and μ(MoKα) = 1.181 mm-1. The final R = 0.0425 and wR = 0.1001 for 7002 independent reflections. The title complex shows a mononuclear Ru(Ⅱ)capped by an η5-Cp ring, a chelating η2-dppc and a terminal chloride to assume a three-legged piano-stool configuration.     

Synthesis and Crystal Structure of {η5: η1-[ (2-Methoxyphenyl)-isopropyl]-indenyl}(dimethoxyethylene)lithium

The title compound {η5:η1-[(2-MeOC6H4)C3H6]C9H6}Li(DME) (DME = 1,2-dimethoxy-ethylene) was synthesized by the treatment of 3-[(2-methoxyphenyl)-isopropyl]-indene with 1 equiv. of n-BuLi followed by the recrystallization from a mixed solution of toluene and DME.The compound crystallizes in orthorhombic system, pace group Pbca with a = 14.5677(3), b = 15.54670(10), c = 18.7498(3) (A), Z = 8, V = 4246.45(11) (A)3, Dc = 1.127 g/cm3 andμ(MoKα) = 0.072 mm- 1. The coordination geometry can be described as a distorted tetrahedron.     

Synthesis of [μ-methyllenebis(η5-3-tert-butyl-2-methylinden-1-yl)dichlorozirconium(IV)]

An efficient synthetic approach to 3-alkyl(aryl)-2-bromoindenes was developed. The reaction of 2-bromo-3-tert-butylindene with MeMgl catalyzed by Ni(dppp)Cl₂ afforded 3-tert-butyl-2-methylindene from which bis(3-tert-butyl-2-methylinden-1-yl)methane and the correspondingansa-zirconocene were synthesized.     

Synthesis and structure of η6-(biphenyl)-η5- (cyclopentadienyl)iron(II) hexaflourophosphates

A series of η⁶-(biphenyl)-η⁵-(cyclopentadienyl)iron(II) hexafluorophosphates have been prepared. Demethylation occured during the synthesis of the 2′-OMe derivatives to yield the correspoding 2′-OH product. The mechanism of this process is discussed. In all cases the complexation involved the unsubstituted phenyl ring. From ¹³C NMR data, values of Hammett resonance parameters σ_R, were calculated which show that the [CpfeC₆H₅]⁺ group behaves as an electron-withdrawing substituent comparable in strength to the cyano group. Approximate values of the biphenyl interplanar angle (θ) were obtained. θ appeared to be significantly lower when electron-releasing substituents were present. ⁵⁷ Fe Mössbauer data support the strong electron acceptor properties of the [CpFe⁺C₆H₅] moiety. In particular the quadrupole splitting (QS) shows a marked increase for the 4-OMe derivative relative to the unsubstituted comples. This is in direct contrast to the aryl ferrocenes. Here, the ferrocenyl and OMe substituents are electronically and so there is no (QS) enhancement.     

Synthesis and Structure of μ-Oxobis[triphenyl(furfuraloximato)antimony(V)]

Reaction of triphenylstibine with furfuraloxime in the presence of hydrogen peroxide in water-ether solution forms -oxobis[triphenyl(furfuraloximato)antimony(V)] in 90% yield. This complex has a dimeric structure in which two antimony atoms are bound with the bridge oxygen atom and two bridge oxime groups coordinating the metal atom by the oxygen as well as by the nitrogen atoms to form bicyclo[2.2.1]heptane fragment. SbOSb angle is 125.5(3)°, the bonds between the antimony atom and the bridge oxygen atoms [1.957(6) and 1.946(5) Å] are shorter than with the oxygen atoms of oxime groups [2.146(6) and 2.148(6) Å].     

Synthesis and Crystal Structure of Bis[a-chloro-(o-chloro-benzylidene)] Hydrazine

1 INTRODUCTION The azine derivatives are useful compounds because of their special properties. On the one hand, the azines and ,-dichloro-azines are very impor- tant intermediates[1, 2] for synthesizing s-tetrazines which have some peculiar properties, s…     

Syntheses and Structures of μ-Oxo-Bis[dichloroiron(III)]-Bis-[2,6-Diacetylpyridinedioximate(-1)]Iron(II) and Related Compounds

The syntheses and structures of four new compounds are described. Two of these compounds are the anhydrous and dihydrate chloride salts of the diamagnetic bis(2,6-diacetylpyridinedioxime)iron(II) cation, [Fe(DAPDH₂)₂]²⁺. In this complex cation the DAPDH₂ ligand binds to the iron, as expected, through its three nitrogen atoms leaving the four oxime oxygen atoms protonated and uncoordinated. The third compound is (AsPh₄)₂[Fe₂OCl₆], a new salt of the well-known oxo-bridged diiron complex, [Fe₂OCl₆]^2?. The synthesis of (AsPh₄)₂[Fe₂OCl₆] is a high yield, straightforward, one-step preparation starting with AsPh₄Cl and ferrous chloride in methanol. In this synthesis Fe(II) is oxidized to Fe(III) by atmospheric O₂. The fourth new compound is the novel and unexpected triiron complex [Fe(DAPDH)₂Fe₂OCl₄]. This complex is derived from [Fe(DAPDH₂)₂)]²⁺ and [Fe₂OCl₆]^2? by removing the H⁺ from each of two adjacent oxime oxygen atoms of the former and one Cl^? from each of the Fe(III) ions of the latter. The resulting neutral fragments, Fe(DAPDH)₂ and Fe₂OCl₄, are joined via bonds linking the two oxime oxygen atoms to the two Fe(III) ions giving rise to an unusual eight membered chelate ring containing three iron ions, two nitrogen atoms and three oxygen atoms, one of which is the bridge between the two Fe(III) ions.     

Synthesis,characterization, and reactivity of ruthenium(II) complexes containing η6-arene-η1-pyrazole ligands

New ruthenium(II) complexes containing η⁶-arene-η¹-pyrazole ligands were synthesized and characterized by elemental analysis and spectroscopic methods. In addition, the molecular structure of dichloro-3,5-dimethyl-1-(pentamethylbenzyl)-pyrazole–ruthenium(II), [Ru]L_3b, was determined by X-ray diffraction studies. These complexes were applied in the transfer hydrogenation of acetophenone by isopropanol in the presence of potassium hydroxide. The activities of the catalysts were monitored by NMR.     

Synthesis and Crystal Structure of Bis[α-chloro-(o-chloro-benzylidene)] Hydrazine

The title compound bis[α-chloro-(o-chloro-benzylidene) hydrazine] (C14H8Cl4N2, Mr = 346.02) has been prepared, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 10.777(2), b = 6.456(2), c = 10.988(3) A, β = 90.48(2)o, V = 764.5(3) A3, Z = 2, Dc = 1.503 g/cm3, F(000) = 348 and μ(MoKα) = 0.763 mm-1 (λ = 0.71073 A). The structure was refined to R = 0.0793 and wR = 0.2398 for 1694 observed reflections with I > 2σ(I). The results of crystal structure determination show that both C(7) and C(7)a are of sp2 hybridization and there exists electronic conjugation in the aza-diene of -C=N-N=C.     

Synthesis,Structure and Biological Activities of S-[α-(4-Methoxyphenylcarbonyl)-2-(1,2,4-triazole-1-yl)] ethyl-N,N-dime-thyldithiocarbamate

IntroductionAsanimportanttypeoffungicides ,triazolecom poundsarehighlyefficient,lowpoisonousandinwardab sorbent.1 3Atpresent,thestudiesontriazolederivativesaremainlyconcentratedoncompoundswithtriazoleastheonlyactivegroup .Therearefewreportsoftriazolecom poundsthatcontainbothtriazolegroupandotheractivegroupinasinglemolecule .Dialkyl substituteddithiocar bamatesaltshavealsoshowninterestingbiologicalef fects .4 N ,N Dialkyldithiocarbamatehasbeenknownasbroad rangefungicidesandhavingdifferentfung…     

The Superbulky Pn Ligand Complexes [CpBIGFe(η5−P5)] and [(CpBIGFe)2(μ,η4:4-P4)]—Synthesis and Characterization

Abstract

A new synthesis of [Cp^BIGFe(CO)₂]₂ 3 (Cp^BIG = C₅(4-ⁿBuC₆H₄)₅) was developed starting from Cp^BIGNa and FeCl₂ in the presence of CO. Reaction of this product with P₄ leads to the two new P_n ligand complexes [Cp^BIGFe(η⁵-P₅)] 1b and [(Cp^BIGFe)₂(μ,η^4:4-P₄)] (4) containing the highly sterically demanding Cp^BIG ligand. Depending on the solvent, different ratios of 1b:4 are obtained. The products 1b, 3, and 4 were characterized by spectroscopic methods as well as by X-ray diffraction.     

Synthesis and Crystal Structure of [K(18-Crown-6)]_3P_(11)·2en

1 INTRODUCTIONSince the first report on the reduction of lead by sodium to a green solution in 1891 by Johannis, polyanionic clusters of post-transition metals known as Zintl ions have attracted much attention in chemistry due to their beautiful molecules, diverse reactivity and potential applications[1, 2]. Polyphos- phide anions represent one of the most important classes of zintl ions. The binary alkali-metal poly- phosphides, such as MI4P6 (M = K, Rb, Cs)[3～5], MI3P7 (M = Li-Cs)…     

Synthesis and Crystal Structure of Bis[(2,6-pyridinedicarboxylato)(methanol)dibenzyltin(IV)]

ＩｎｔｒｏｄｕｃｔｉｏｎＤｉｏｒｇａｎｏｔｉｎｄｅｒｉｖａｔｉｖｅｓｏｆ 2 ,6 ｐｙｒｉｄｉｎｅｄｉｃａｒｂｏｘｙｌｉｃａｃｉｄｅｘｈｉｂｉｔｈｉｇｈｉｎｖｉｔｒｏａｎｔｉｔｕｍｏｕｒａｃｔｉｖｉｔｉｅｓ .1 5Ｔｈｅｓｅｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｚｅｄｂｙｔｈｅｒｅａｃｔｉｏｎｏｆｄｉｏｒｇａｎｏｔｉｎｄｉｃｈｌｏｒｉｄｅｓｏｒｄｉｏｒｇａｎｏｔｉｎｏｘｉｄｅｓｗｉｔｈ 2 ,6 ｐｙｒｉｄｉｎｅｄｉｃａｒｂｏｘｙｌｉｃａｃｉｄ ,ｂｕｔｔｈｅｒｅａｃｔｉｏｎｂｅｔｗｅｅｎｔｒｉ …     

Synthesis and Crystal Structure of Bis-{N-[2-(6-ethylpyridyl)]-salicylideneiminato} Cobalt(Ⅱ)

1 INTRODUCTION The Schiff bases derived from salicylaldehyde and 2-aminopyridine derivatives have been used as potentially terdentate ligands[1]. Yamada and Yam- anouchi have synthesized the type of ML2nH2O complexes (M = CoⅡ, NiⅡ, CuⅡ, ZnⅡ or PdⅡ)[     

Synthesis and Crystal Structure of Potassium Triethylenetetraaminehexaacetatodi [Oxo-vanadium(Ⅳ)] Hexahydrate, K_2[V_2O_2(ttha)]·6(H_2O)

1 INTRODUCTION Interest in vanadium in the physiology and biochemistry has promoted enormously in recent years. Vanadium is known to exist in alternative nitrogenase metalloenzyme systems fixing nitrogen. It is also found to participate in biological processes exhibiting mitogenic behavior and enzyme inhi- bition[1]. Up to date, several crystal structures have been reported about vanadium with carboxylic or polycarboxylic acid[2, 3]. However, very few struc- tures of vanadium complexes …