Super‐Bulky Penta‐arylcyclopentadienyl Ligands: Isolation of the Full Range of Half‐Sandwich Heavy Alkaline‐Earth Metal Hydrides

Hydrogenolysis of the half‐sandwich penta‐arylcyclopentadienyl‐supported heavy alkaline‐earth‐metal alkyl complexes (Cp^Ar)Ae[CH(SiMe₃)₂](S) (Cp^Ar=C₅Ar₅, Ar=3,5‐ⁱPr₂‐C₆H_3; S=THF or DABCO) in hexane afforded the calcium, strontium, and barium metal–hydride complexes as the same dimers [(Cp^Ar)Ae(μ‐H)(S)]₂ (Ae=Ca, S=THF, 2‐Ca ; Ae=Sr, Ba, S=DABCO, 4‐Ae ), which were characterized by NMR spectroscopy and single‐crystal X‐ray analysis. 2‐Ca , 4‐Sr , and 4‐Ba catalyzed alkene hydrogenation under mild conditions (30 °C, 6 atm, 5 mol % cat.), with the activity increasing with the metal size. A variety of activated alkenes including tri‐ and tetra‐substituted olefins, semi‐activated alkene (Me₃SiCH=CH₂), and unactivated terminal alkene (1‐hexene) were evaluated.     

Addition Reactions of Me3SiCN with Aldehydes Catalyzed by Aluminum Complexes Containing in their Coordination Sphere O,S, and N Ligands

The reaction of one equivalent of LAlH₂ ( 1 ; L=HC(CMeNAr)₂, Ar=2,6‐iPr₂C₆H₃, β‐diketiminate ligand) with two equivalents of 2‐mercapto‐4,6‐dimethylpyrimidine hydrate resulted in LAl[(μ‐S)(m‐C₄N₂H)(CH₂)₂]₂ ( 2 ) in good yield. Similarly, when N‐2‐pyridylsalicylideneamine, N‐(2,6‐diisopropylphenyl)salicylaldimine, and ethyl 3‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐2‐carboxylate were used as starting materials, the corresponding products LAl[(μ‐O)(o‐C₆H₄)CN(C₅NH₄)]₂ ( 3 ), LAlH[(μ‐O)(o‐C₄H₄)CN(2,6‐iPr₂C₆H₃)] ( 4 ), and LAl[(μ‐NH)(o‐C₈SH₈)(COOC₂H₅)]₂ ( 5 ) were isolated. Compounds 2 – 5 were characterized by ¹H and ¹³C NMR spectroscopy as well as by single‐crystal X‐ray structural analysis. Surprisingly, compounds 2 – 5 exhibit good catalytic activity in addition reactions of aldehydes with trimethylsilyl cyanide (TMSCN).     

Structural Investigation of New Lithium Amidinates and Guanidinates

A series of potentially useful lithium amidinates and guanidinates were prepared and fully characterized. Treatment of N,N′‐diisopropylcarbodiimide with phenyllithium in diethyl ether afforded the lithium amidinate [PhC(NiPr)₂Li(OEt₂)]₂ ( 1 ). Similar treatment of N,N′‐diorganocarbodiimides R′–N=C=N–R′ [R′ = iPr, cyclohexyl (Cy)] with secondary lithium amides LiNR₂ [R₂ = Et₂, iPr₂, (CH₂)₄] followed by crystallization from THF or 1,4‐dioxane gave the lithium guanidinates [R₂NC(NR′)₂Li(S)]₂ [ 2 : R = Et, R′ = iPr, S = THF; 3 : R₂ = (CH₂)₄, R′ = iPr, S = THF; 4 : R = R′ = iPr, S = ½ 1,4‐dioxane; 5 : R₂ = (CH₂)₄, R′ = Cy, S = 1,4‐dioxane] as crystalline solids. Reaction of N‐lithioaziridine with the corresponding carbodiimides afforded solvent‐deficient [{C₂H₄NC(NiPr₂)₂}₂Li₂(THF)]₂ ( 6 ), and [C₂H₄NC(NEt)(NtBu)Li(THF)]₂ ( 7 ). Crystal structure determination revealed the presence of common ladder‐type dimeric structures for 1 – 5 . Compound 6 exists as a dimer of two ladder‐type dimers in the crystal, and 7 exhibits an unusual dimeric structure comprising an eight‐membered C₂N₄Li₂ ring.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

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.     

Synthesis of Lanthanide–Alkylaluminium Bimetallic Complexes and Studies on Their Catalytic Activities for Polymerization of Some Polar Monomers

Three new lanthanide (Ln)–alkylaluminium (Al) bimetallic complexes with the formula [(μ-CF₃CO₂)₂Ln(μ-CF₃CHO₂)AlR₂ · 2THF]₂ (Ln=Nd, Y, R=i-C₄H₉ (i-Bu); Ln=Eu, R=C₂H₅(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF₃CO₂)₃ (Ln=Nd, Y) with HAl (i-Bu)₂ and of Eu(CF₃CO₂)₃ with AlEt₃, respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(μ-CF₃CO₂)₂Nd (μ-CF₃CHO₂)Al(i-Bu)₂ · 2THF]₂ (Nd–Al) and [(μ-CF₃CO₂)₂Y(μ-CF₃CHO₂)Al(i- Bu)₂ · 2THF]₂ (Y–Al) are isomorphous and crystallize in space group P 1 with a =12.441(3) Å [12.347(5) Å for Y–Al], b =12.832(3) Å [12.832(4) Å], c =11.334(3) Å [11.292(8) Å], α=104.93 (2)° [104.45(4)°], β=98.47(2)° [98.81(4)°], γ=64.60(2)° [64.30(3)°], R =0.519 [0.113], R _w=0.0532 [0.110], Z =1 and [(μ-CF₃CO₂)₂Eu(CF₃ CHO₂)AlEt₂ · 2THF]₂(Eu–Al) in space group P 2₁/ n with a =11.913(6) Å, b =14.051(9) Å, c =17.920(9) Å, α=101.88(11)°, β=γ=90°, R =0.0509, R _w=0.0471 and Z =2. The six CF₃CO     

Synthesis and Structural Characterization of New Divanada‐ and Diniobaboranes Containing Chalcogen Atoms

The reaction of [Cp_nMCl_4?x] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=η⁵‐C₅H₅) with LiBH₄ ? THF followed by thermolysis in the presence of dichalcogenide ligands E₂R₂ (E=S, Te; R=2,6‐(tBu)₂‐C₆H₂OH, Ph) and 2‐mercaptobenzothiazole (C₇H₅NS₂) yielded dimetallaheteroboranes [{CpV(μ‐TePh)}₂(μ₃‐Te)BH ? thf] ( 1 ), [(CpV)₂(BH₃S)₂] ( 2 ), [(CpNb)₂B₄H₁₀S] ( 3 ), [(CpNb)₂B₄H₁₁S(tBu)₂C₆H₂OH] ( 4 ), and [(CpNb)₂B₄H₁₁TePh] ( 5 ). In cluster 1 , the V₂BTe atoms define a tetrahedral framework in which the boron atom is linked to a THF molecule. Compound 2 can be described as a dimetallathiaborane that is built from two edge‐fused V₂BS tetrahedron clusters. Cluster 3 can be considered as an edge‐fused cluster in which a trigonal‐bipyramidal unit (Nb₂B₂S) has been fused with a tetrahedral core (Nb₂B₂) by means of a common Nb₂ edge. In addition, thermolysis of an in‐situ‐generated intermediate that was produced from the reaction of [Cp₂VCl₂] and LiBH₄ ? THF with excess BH₃ ? THF yielded oxavanadaborane [(CpV)₂B₃H₈(μ₃‐OEt)] ( 6 ) and divanadaborane cluster [(CpV)₂B₅H₁₁] ( 7 ). Cluster 7 exhibits a nido geometry with C_2v symmetry and it is isostructural with [(Cp*M)₂B₅H_9+n] (M=Cr, Mo, and W, n=0; M=Ta, n=2; Cp*=η⁵‐C₅Me₅). All of these new compounds have been characterized by ¹H NMR, ¹¹B NMR, and ¹³C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of compounds  1 – 4 , 6 , and 7 .     

1,1‐Diethyl‐1‐germa‐2,3,4,5‐tetra‐tert‐butyl‐2,3,4,5‐tetraphospholan (C2H5)2Ge(tBuP)4, Molekül‐ und Kristallstruktur

1,1‐Diethyl‐1‐germa‐2,3,4,5‐tetra‐ tert ‐butyl‐2,3,4,5‐tetraphospholane (C₂H₅)₂Ge( t BuP)₄, Molecular and Crystal Structure The reaction of the diphosphide K₂[(tBuP)₄] · THF ( 1 ) with the germanium(IV) compound (C₂H₅)₂GeCl₂ leads via a [4 + 1]‐cyclo‐condensation reaction to 1,1‐diethyl‐1‐germa‐2,3,4,5‐tetra‐tert‐butyl‐2,3,4,5‐tetraphospholane (C₂H₅)₂Ge(tBuP)₄ ( 2 ) with the 5‐membered GeP₄ ring system. 2 could be characterized ³¹P NMR spectroscopically, mass spectrometrically and by a single crystal structure analysis.     

新颖双核钐硫酚化合物[(THF)3I2Sm(m-SAr)]2 (Ar = Ph, 4-Me2NC6H4)的合成与化合物[(THF)3I2Sm(m-S-4-Me2NC6H4)]2的晶体结构

Reactions of SmI2 in THF with ArSSAr produced two binuclear samarium thiolate complexes [（THF）3I2- Sm（μ-SAr）]2 [Ar=Ph （1）, 4-Me2NC6H4 （2）] in high yields. The structure of 2 was characterized by single crystal X-ray crystallography. The crystal of 2 belongs to the triclinic system with space group P 1 and a=0.95705（13） nm, b= 1.22287（14） nm, c= 1.26450（14） nm, a=64.194（11）°, B=78.491（13）°, y=76.176（12）°, V= 1.2860（3） nm^3, Z= 1,μ=4.783 mm^-1, Dc= 1.964 Mg/m^3, M= 1521.19, S= 1.046, R1=0.0358, wR2=0.0910. X-ray analysis revealed that 2 is a thiolate-bridged dimer in which each Sm atom adopts a distorted pentagonal bipyramidal coordi- nation geometry.     

Nickel as a Lewis Base in a T‐Shaped Nickel(0) Germylene Complex Incorporating a Flexible Bis(NHC) Ligand

Flexible, chelating bis(NHC) ligand 2 , able to accommodate both cis‐ and trans‐coordination modes, was used to synthesize ( 2 )Ni(η²‐cod), 3 . In reaction with GeCl₂, it produced ( 2 )NiGeCl₂, 4 , featuring a T‐shaped Ni⁰ and a pyramidal Ge center. Complex 4 could also be prepared from [( 2 )GeCl]Cl, 5 , and Ni(cod)₂, in a reaction that formally involved Ni–Ge transmetalation, followed by coordination of the extruded GeCl₂ moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the Ni→Ge bond is formed through σ‐donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)₂Ni(cod) complexes 9 and 10 , as well as (NHC)₂GeCl₂ derivative 11 , incorporating ligands that cannot accommodate a wide bite angle, failed to produce isolable Ni–Ge complexes. The isolation of ( 2 )Ni(η²‐Py), 12 , provides further evidence for the reluctance of the ( 2 )Ni⁰ fragment to act as a σ‐Lewis acid.     

Isolation and Ambident Reactivity of a Chlorogermylenoid

Treatment of 2,5‐di(3,5‐tert‐butylphenyl)‐1‐lithioferrocene with GeCl₂?dioxane afforded the corresponding chlorogermylenoid that exhibited an ambident reactivity in different solvents; it displayed a behavior characteristic for a dichlorogermylene anion in THF, while it exhibited the typical reactivity of a chlorogermylene in toluene. X‐Ray diffraction analysis of a single crystal of this chlorogermylenoid, obtained from recrystallization in THF, revealed a separated‐ion‐pair structure in the solid state.     

Uber die Reaktionen der Hexacarbonyle der VI. Nebengruppe mit Zinn (II)- und Germanium (II)-halogeniden

On Reactions of Subgroup. VI. Hexacarbonyls with Tin(II) and Germanium (II) Halides The neutral complexes M(CO)₅SnX₂ and M(CO)₅GeCl₂ (M = Cr, Mo, W; X = Cl, Br, J) have been prepared by a photochemical reaction between M(CO)₆ and SnX₂, or CsGeCl₃ in THF. The reaction of these compounds with [N(CH₃)₄]X (X = Cl, Br, J) in THF was found to lead to a series of anions [M(CO)₅SnX₃]^? or [M(CO)₅GeCl₃]^? (M = Cr, Mo, W; X = Cl, Br, J), some of which have previously been prepared. The physical properties and IR-spectra of the above compounds are discussed.     

Isolable Boron Persulfide: Activation of Elemental Sulfur with a 2‐Chloro‐Azaborolyl Anion

The novel boron persulfide 2 LB(η²‐S₂) (L=[ArNC(R)CHC(R)]^?; Ar=2,6‐Me₂C₆H₃, R=tBu) was obtained by the reaction of the 2‐chloro‐azaborolyl anion 1 (LBCl)K(THF) with 0.25 equiv of elemental sulfur (S₈). Persulfide 2 is labile in solution and could be converted to the cyclic tetrasulfide LBS₄ ( 3 ) and hexasulfide LBS₆ ( 4 ) in the presence of sulfur at room temperature and 50 °C, respectively. Desulfination of 2 with triphenylphosphine resulted in the formation of the thioxoborane LB=S ( 5) . Alternatively, 3 and 4 could be obtained by the reaction of 1 with an excess of sulfur. Structural analysis of 2 disclosed the relatively long S?S bond of 2.1004(8) Å due to the lone‐pair repulsions of the two sulfur atoms, as disclosed by DFT calculations.     

Synthesis and Characterization of Monomeric Salicylaldiminato Lanthanide Complexes and Their Catalytic Behavior for Polymerization of ε—Caprolactone

IntroductionSchiffbaseligandscanbeusedtoprovideastereochem icallyrigidligandframeworkinhomogenousprecatalystsofsomemetals,suchassalenCrcatalystsinasymmetricring openingreactionofepoxide1andsalenAlinring openingpolymerizationoflactideandrelatedcyclicesters .2 Recently ,itwasreportedthatthebidentateSchiffbasecomplexesofearlyandlatetransitionmetalscanserveaspromisingalterna tivestometallocenecatalystsforthepolymerizationofα olefins.3Therefore ,theapplicationsofSchiffbaseligandsinorganometallic…     

A Novel Divalent Ytterbium Complex Supported by a Bridged Diamide Ligand: Synthesis and Structure of [{Me2Si(NPh)2Yb(THF)2}(μ3‐Cl)(μ4‐Cl){Li(THF)}2]2·2THF

The reaction of anhydrous YbCl₃ with 1 equiv. of Li₂Me₂Si(NPh)₂ in THF, after workup, yielded a ytterbium(III) chloride [{Me₂Si(NPh)₂Yb}(μ₂‐Cl)(TMEDA)]₂·3PhMe ( 1 ) (TMEDA=tetramethylethanediamine). The same reaction followed by treatment with Na‐K alloy afforded a new ytterbium(II) complex supported by a bridged diamide with four coordinated LiCl molecules, [{Me₂Si(NPh)₂Yb(THF)₂}(μ₃‐Cl)(μ₄‐Cl){Li(THF)}₂]₂·2THF ( 2 ) in high yield. Both complexes were structurally characterized by X‐ray analysis to be dimers. Complex 1 was a chlorine‐bridged dimer with ytterbium in a distorted octahedral geometry. In complex 2 two [Me₂Si(NPh)₂Yb(THF)₂]‐(μ₃‐Cl)[Li(THF)]₂ moieties were connected with each other by two μ₄‐Cl bridges to form a "chair‐form" framework.     

Synthesis of ferrocene‐containing N‐aryloxo β‐ketoiminate lanthanide complexes and polymerization of ε‐caprolactone

The synthesis, characterization and ε‐caprolactone polymerization behavior of lanthanide amido complexes stabilized by ferrocene‐containing N‐aryloxo functionalized β‐ketoiminate ligand FcCOCH₂C(Me)N(2‐HO‐5‐Bu^t‐C₆H₃) (LH₂, Fc = ferrocenyl) are described. The lanthanide amido complexes [LLnN(SiMe₃)₂(THF)]₂ [Ln = Nd ( 1 ), Sm ( 2 ), Yb ( 3 ), Y ( 4 )] were synthesized in good yields by the amine elimination reactions of LH₂ with Ln[N(SiMe₃)₂]₃(µ‐Cl)Li(THF)₃ in a 1:1 molar ratio in THF. These complexes were characterized by IR spectroscopy and elemental analysis, and ¹H NMR spectroscopy was added for the analysis of complex 4 . The definitive molecular structures of complexes 1 and 3 were determined by X‐ray diffraction studies. Complexes 1 – 4 can initiate the ring‐opening polymerization of ε‐caprolactone with moderate activity. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and characterization of heterobimetallic oxo-bridged aluminum-rare earth metal complexes

Reaction of the aluminum hydroxide LAl(OH)[C(Ph)CH(Ph)] (1, L = HC[(CMe)(NAr)](2), Ar = 2,6-iPr(2)C(6)H(3)) with Y(CH(2)SiMe(3))(3)(THF)(2) yielded the oxo-bridged heterobimetallic yttrium dialkyl complex LAl[C(Ph)CH(Ph)](μ-O)Y(CH(2)SiMe(3))(2)(THF)(2) (2). Alkane elimination reaction of 2 with 2-(imino)pyrrole [NN]H ([NN]H = 2-(ArN═CH)-5-tBuC(4)H(2)NH) afforded the yttrium monoalkyl complex LAl[C(Ph)CH(Ph)] (μ-O)Y(CH(2)SiMe(3))[NN](THF)(2) (5). Alternatively, 5 can be prepared in high yield by reaction of 1 with [NN]Y(CH(2)SiMe(3))(2)(THF)(2) (3). The analogous samarium alkyl complex LAl[C(Ph)CH(Ph)](μ-O)Sm(CH(2)SiMe(3))[NN](THF)(2) (6) was prepared similarly. Reactions of 5 and 6 with 1 equiv of iPrOH yielded the corresponding alkoxyl complexes 7 and 8, respectively. The molecular structures of 3, 6, and 8 have been determined by X-ray single-crystal analysis. Complexes 2, 3, 5, 7, and 8 have been investigated as lactide polymerization initiators. The heterobimetallic alkoxyl 8 is highly active to yield high molecular weight (M(n) = 6.91 × 10(4)) polylactides with over 91% conversion at the lactide-to-initiator molar ratio of 2000.     

Synthesis and characterization of aluminum-containing tin(IV) heterobimetallic sulfides

Three novel aluminum-containing tin(IV) heterobimetallic sulfides are reported. The reaction of [LAl(SLi)2(THF)2]2 (1) [L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3] with Ph2SnCl2, Me2SnCl2, and SnCl4 in THF respectively afforded LAl(mu-S)2SnPh2 (2), LAl(mu-S)2SnMe2 (3), and LAl(mu-S)2Sn(mu-S)2AlL (4) in moderate yields. Compounds 2, 3, and 4 were characterized by elemental analysis, NMR, electron-impact mass spectrometry, and single-crystal X-ray structural analysis.     

SYNTHESIS AND STRUCTURE OF A PENTAMETHYLCYCLOPENTADIENYL THULIUMCHLORIDE COMPLEX, [(C5ME5)2Tm(μ3-CL)2K(THF)]N

Abstract

The first structural data on a pentamethylcyclopentadienyl complex ofthulium, [(C₅Me₅)₂Tm(μ₃-C1)₂K(THF)]_n,1, are reported. TmCl₃ reacts with 2 equivalents ofKC₅Me₅ in THF to form 1 in <80% yield. 1 crystallizes from THF/hexanes in thespace group Cc with a = 11.1491(13) Å, b= 28.107(2) Å, c = 8.5921(8) Å, β= 102.485(8)°, V = 2628.8(4) ų, and D_calcd = 1.570 Mg/m³ for Z= 4. Least-squares refinement of the model based on 3114reflections (F² > 3.0 [sgrave] (F²))converged to a final R_F = 1.9%. Thepolymeric structure of 1 is generated by triply bridgingchlorides, each of which is connected to one(C₅Me₅)₂Tm bentmetallocene unit and two K(THF) moieties in a T-shaped geometryaround the chloride.     

Synthese und Struktur der Komplexe [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 und [(n‐Bu)4N]2[Pd3Cl8]

Synthesis and Crystal Structure of the Complexes [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂PdCl₂], [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ and [(n‐Bu)₄N]₂[Pd₃Cl₈] The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂ PdCl₂] ( 1 ) is obtained in THF by the reaction of PdCl₂(NCC₆H₅)₂ with [(n‐Bu)₄N][ReNCl₄] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl₂ instead of PdCl₂(NCC₆H₅)₂, orange crystals of hitherto unknown [(n‐Bu)₄N]₂[Pd₃Cl₈] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl₄Re≡N}₂PdCl₂]^2— a linear PdCl₂ moiety is connected in trans arrangement with two complex fragments [(THF)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd₃Cl₈]^2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph₄P][ReNCl₄] and PdCl₂(NCC₆H₅)₂ in THF brown crystals of the heterometallic complex, [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ ( 2 ) result. 2 crystallizes in the monoclinic space group P2₁/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)₂PdCl of the centrosymmetric anionic complex [(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂^2— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl₄Re≡N]^— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm.