Synthese und Charakterisierung donor-funktionalisierter ansa-Metallocene von Yttrium,Neodym, Samarium,Erbium und Lutetium

Organometallic Compounds of the Lanthanides. 133 Synthesis and Characterization of donor-functionalised ansa -Metallocenes of Yttrium, Neodymium, Samarium, Erbium, and Lutetium The reaction of Me₂SiCl₂ with K[C₅H₄^tBu], Li[C₅H₄SiMe₃] or K[C₅H₃^tBuMe-3] followed by treatment with K[C₅H₄CH₂CH₂NMe₂] yields mixed substituted dicyclopentadienyldimethylsilanes which after double deprotonation with KH afford the dipotassium salts K₂[Me₂Si(C₅H₃^tBu-3)(C₅H₃CH₂CH₂NMe₂-3)] ( 1 ), K₂[Me₂Si · (C₅H₃SiMe₃-3)(C₅H₃CH₂CH₂NMe₂-3)] ( 2 ), and K₂[Me₂Si · (C₅H₂^tBu-3-Me-5)(C₅H₃CH₂CH₂NMe₂-3)] ( 3 ), respectively. The reaction of 1 , 2 , or 3 with LnCl₃(THF)_x (Ln = Y, La, Nd, Sm, Er, Lu) leads to the complexes [Me₂Si(C₅H₃^tBu-3) · (C₅H₃CH₂CH₂NMe₂-3)]LnCl [Ln = Y ( 4 a ), Sm ( 4 c ), Lu ( 4 e )], [Me₂Si(C₅H₃SiMe₃-3)(C₅H₃CH₂CH₂NMe₂-3)]LnCl [Ln = Y ( 5 a ), Sm ( 5 c ), Lu ( 5 e )], and [Me₂Si(C₅H₂^tBu-3-Me-5)(C₅H₃CH₂CH₂NMe₂-3)]LnCl [Ln = Y ( 6 a ), Nd ( 6 b ), Sm ( 6 c ), Er ( 6 d ), Lu ( 6 e )], respectively. Alkylation of 4 a , 4 c , 5 a , and 6 b , 6 e with LiCH₃, LiCH₂SiMe₃, and LiCH(SiMe₃)₂ produces the alkylmetallocenes [Me₂Si(C₅H₃^tBu-3) · (C₅H₃CH₂CH₂NMe₂-3)]LnR [R = CH₃, Ln = Y ( 7 a ), Sm ( 7 c ); R = CH₂SiMe₃, Ln = Y ( 8 a )], [Me₂Si(C₅H₃SiMe₃-3) · (C₅H₃CH₂CH₂NMe₂-3)]YCH₃ ( 9 a ), and [Me₂Si(C₅H₂^tBu3-Me-5)(C₅H₃CH₂CH₂NMe₂-3)]LnR (R = CH₃, Ln = Lu ( 10 e ); R = CH₂SiMe₃, Ln = Lu ( 11 e ); R = CH(SiMe₃)₂, Ln = Nd ( 12 b ), Lu ( 12 e )], respectively. All new compounds were characterized by elemental analyses, NMR spectroscopy and mass spectrometry. The molecular structure of 6 c and 6 e was determined by single crystal X-ray structure analysis.     

Synthesis,Structures, and Properties of Lanthanide Complexes with Pyrimidine‐2‐carboxylic Acid

Six lanthanide complexes [Ln(pmc)₂NO₃]_n [Hpmc = pyrimidine‐2‐carboxylic acid, Ln = La ( 1 ), Pr ( 2 )], [Ln(pmc)₂(H₂O)₃]NO₃ · H₂O [Ln = Eu ( 3 ), Tb ( 4 ) Dy ( 5 ), Er ( 6 )] were synthesized by the reactions of lanthanide nitrate and pyrimidine‐2‐carboxylic acid in water at room temperature. These complexes were characterized by single‐crystal X‐ray diffraction analysis, elemental analysis, IR, circular dichroism (CD) and fluorescence spectra. Structure analysis shows that complexes 1 and 2 are isostructural with P4₃2₁2 space group, whereas isostructural complexes 3 – 6 belong to the P2₁/c space group. In complexes 1 and 2 , the central metal atoms are coordinated by nitrates and pmc^–, which are self‐assembled to construct a 3D porous network with 6₂.6₂.6₂.6₂.6₂.6₂ (6⁶) topology. In complexes 3 – 6 , H₂O and pmc^– ligands are coordinated and the complexes exhibit a one‐dimensional zigzag chain, which is further expanded into a 3D structure by hydrogen bonding. In addition, the circular dichroism of 1 and 2 proves that the two complexes are both chiral with achiral ligand of Hpmc. Luminescent measurements of compounds 3 – 5 indicate that the characteristic fluorescence of Eu³⁺, Tb³⁺, and Dy³⁺ are observed.     

Synthesis and Structures of ansa‐Titanocene Complexes with Diatomic Bridging Units for Overall Water Splitting

The synthesis of a series of ansa‐titanocene dichlorides [Cp′₂TiCl₂] (Cp′=bridged η⁵‐tetramethylcyclopentadienyl) and the corresponding titanocene bis(trimethylsilyl)acetylene complexes [Cp′₂Ti(η²‐Me₃SiC₂SiMe₃)] is described. The ethanediyl‐bridged complexes [C₂H₄(C₅Me₄)₂TiCl₂] ( 2 ‐Cl₂) and [C₂H₄(C₅Me₄)₂Ti(η²‐Me₃SiC₂SiMe₃)] ( 2‐ btmsa; btmsa=η²‐Me₃SiC₂SiMe₃) can be obtained from the hitherto unknown calcocenophane complex [C₂H₄(C₅Me₄)₂Ca(THF)₂] ( 1 ). Furthermore, a heterodiatomic bridging unit containing both, a dimethylsilyl and a methylene group was introduced to yield the ansa‐titanocene dichloride [Me₂SiCH₂(C₅Me₄)₂TiCl₂] ( 3 ‐Cl₂) and the bis(trimethylsilyl)acetylene complex [Me₂SiCH₂(C₅Me₄)₂Ti(η²‐Me₃SiC₂SiMe₃)] ( 3 ‐btmsa). Besides, tetramethyldisilyl‐ and dimethylsilyl‐bridged metallocene complexes (structural motif 4 and 5 , respectively) were prepared. All ansa‐titanocene alkyne complexes were reacted with stoichiometric amounts of water; the hydrolysis products were isolated as model complexes for the investigation of the elemental steps of overall water splitting. Compounds 1 , 2 ‐btmsa, 2 ‐(OH)₂, 3 ‐Cl₂, 3 ‐btmsa, 4 ‐(OH)₂, 3 ‐alkenyl and 5 ‐alkenyl were characterised by X‐ray diffraction analysis.     

Organometallic Compounds of the Lanthanides. 157 [1] The Molecular Structure of Tris(trimethylsilylmethyl)samarium, ‐erbium, ‐ytterbium,and ‐lutetium

SmCl₃ reacts with Me₃SiCH₂Li in THF yielding Sm(CH₂SiMe₃)₃(THF)₃ ( 1 ). The single crystal X‐ray structural analyses of 1 , Er(CH₂SiMe₃)₃(THF)₂ ( 2 ), Yb(CH₂SiMe₃)₃(THF)₂ ( 3 ), and Lu(CH₂SiMe₃)₃(THF)₂ ( 4 ) show the Sm atom in a fac‐octahedral coordination and the heavier lanthanides Er, Yb, and Lu trigonal bipyramidally coordinated with the three alkyl ligands in equatorial and two THF molecules in axial positions.     

Synthesis and Reactivity of Boron‐, Silicon‐, and Tin‐Bridged ansa‐Cyclopentadienyl–Cycloheptatrienyl Titanium Complexes (Troticenophanes)

A novel one‐pot method was developed for the preparation of [Ti(η⁵‐C₅H₅)(η⁷‐C₇H₇)] (troticene, 1 ) by reaction of sodium cyclopentadienide (NaCp) with [TiCl₄(thf)₂], followed by reduction of the intermediate [(η⁵‐C₅H₅)₂TiCl₂] with magnesium in the presence of cycloheptatriene (C₇H₈). The [n]troticenophanes 3 (n=1), 4 , 8 , 10 (n=2), and 11 (n=3) were synthesized by salt elimination reactions between dilithiated troticene, [Ti(η⁵‐C₅H₄Li)(η⁷‐C₇H₆Li)] ? pmdta ( 2 ) (pmdta=N,N′,N′,N′′,N′′‐pentamethyldiethylenetriamine), and the appropriate organoelement dichlorides Cl₂Sn(Mes)₂ (Mes=2,4,6‐trimethylphenyl), Cl₂Sn₂(tBu)₄, Cl₂B₂(NMe₂)₂, Cl₂Si₂Me₄, and (ClSiMe₂)₂CH₂, respectively. Their structural characterization was carried out by single‐crystal X‐ray diffraction and multinuclear NMR spectroscopy. The stanna[1]‐ and stanna[2]troticenophanes 3 and 4 represent the first heteroleptic sandwich complexes bearing Sn atoms in the ansa bridge. The reaction of 3 with [Pt(PEt₃)₃] resulted in regioselective insertion of the [Pt(PEt₃)₂] fragment into the Sn? C_ipso bond between the tin atom and the seven‐membered ring, which afforded the platinastanna[2]troticenophane 5 . Oxidative addition was also observed upon treatment of 4 with elemental sulfur or selenium, to produce the [3]troticenophanes [Ti(η⁵‐C₅H₄SntBu₂)(η⁷‐C₇H₆SntBu₂)E] ( 6 : E=S; 7 : E=Se). The B? B bond of the bora[2]troticenophane 8 was readily cleaved by reaction with [Pt(PEt₃)₃] to form the corresponding oxidative addition product [Ti(η⁵‐C₅H₄BNMe₂)(η⁷‐C₇H₆BNMe₂)Pt(PEt₃)₂] ( 9 ). The solid‐state structures of compounds 5 , 6 , and 9 were also determined by single‐crystal X‐ray diffraction.     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

Synthesis,Crystal Structures,and Photoluminescence of Lanthanide Coordination Polymers with 4‐Acetamidobenzoate

The reactions of Ln(NO₃)₃ · 6H₂O and 4‐acetamidobenzoic acid (Haba) with 4,4′‐bipyridine (4,4′‐bpy) in ethanol solution resulted in three new lanthanide coordination polymers, namely {[Ln(aba)₃(H₂O)₂] · 0.5(4,4′‐bpy) · 2H₂O}_∞ [Ln = Sm ( 1 ), Gd ( 2 ), and Er ( 3 ), aba = 4‐acetamidobenzoate]. Compounds 1 – 3 are isomorphous and have one‐dimensional chains bridged by four aba anions. 4,4′‐Bipyridine molecules don’t take part in the coordination with Ln^III ions and occur in the lattice as guest molecules. Moreover, the adjacent 1D chains in the complex are further linked through numerous N–H ··· O and O–H ··· O hydrogen bonds to form a 3D supramolecular network. In addition, complex 1 in the solid state shows characteristic emission in the visible region at room temperature.     

Synthesis and Structure of Unprecedented Samarium Complex with Bulky Bis‐iminopyrrolyl Ligand via Intramolecular C=N Bond Activation

An unprecedentate samarium complex of the molecular composition [{κ³‐{(Ph₂CH)N=CH}₂C₄H₂N)}{κ³‐{(Ph₂CHN=CH)(Ph₂CHNCH)C₄H₂N}Sm}₂] ( 2 ), which was isolated by the reaction of a potassium salt of 2,5‐bis{N‐(diphenylmethyl)‐iminomethyl}pyrrolyl ligand [K(THF)₂{(Ph₂CH)N=CH}₂C₄H₂N)] ( 1 ) with anhydrous samarium diiodide in THF at 60 °C through the in situ reduction of imine bond is presented. The homoleptic samarium complex [[κ³‐{(Ph₂CH)–N=CH}₂C₄H₂N)]₃Sm] ( 3 ) can also be obtained from the reaction of compound 1 with anhydrous samarium triiodide (SmI₃) in THF at 60 °C. The molecular structures of complexes 2 and 3 were established by single‐crystal X‐ray diffraction analysis. The molecular structure of complex 2 reveals the formation of a C–C bond in the 2,5‐bis{N‐(diphenylmethyl)iminomethyl}pyrrole ligand moiety (Ph₂Py^–). However, complex 3 is a homoleptic samarium complex of three bis‐iminopyrrolyl ligands. In complex 2 , the samarium ion adopts an octahedral arrangement, whereas in complex 3 , a distorted three face‐centered trigonal prismatic mode of nine coordination is observed around the metal ion.     

Synthesis,Characterization, and Syndio‐Specific Styrene Polymerization of Pyrrolyl‐Substituted Cyclopentadienyl Scandium Complexes

Acid‐base reaction of Sc(CH₂C₆H₄NMe₂‐o)₃ with 1 equiv. of pyrrolyl‐substituted cyclopentadienyl ligand C₄H₂Me₂NSiMe₂C₅Me₄H in toluene gave the half‐sandwich scandium bis(aminobenzyl) complex (C₄H₂Me₂NSiMe₂C₅Me₄)Sc(CH₂C₆H₄NMe₂‐o)₂ ( 2 ). Amine elimination between Sc[N(SiHMe₂)₂]₃(THF) and one equivalent of C₄H₂Me₂NSiMe₂C₅Me₄H afforded the scandium bis(silylamide) complex (C₄Me₂H₂NSiMe₂C₅Me₄)Sc[(NSiHMe₂)₂SiMe₂](THF) ( 3 ). Both scandium complexes 2 and 3 were characterized by elemental analysis, NMR spectroscopy, and single‐crystal X‐ray diffraction. 2 and 3 could serve as highly active precursors for styrene polymerization to give syndio‐tactic polystyrene (rrrrrr > 99 %).     

Tricarbonylrhenium(I) Complexes with N‐Heterocyclic Thiones and Selenols

Reactions of (NEt₄)₂[Re(CO)₃Br₃] with N‐heterocyclic thiols such as 2‐mercaptobenzimidazole (H₂Sbenzim), 2‐mercaptothiazoline (HSthiaz), or 5‐mercapto‐1‐methyltetrazole (HSmetetraz) give rhenium(I) complexes of various compositions: (NEt₄)[Re(CO)₃Br₂(H₂Sbenzim)], [Re(CO)₃(HSthiaz)₃]Br, and (NEt₄)[Re₂(CO)₆(μ‐S‐Smetetraz‐κS)(μ‐N,S‐Smetetraz‐κS,N)₂]. Corresponding reactions with 2‐mercaptopyridine (HSpy) and bis(2‐pyridine)diselenide [(Sepy)₂] did not give defined products in reasonable yields, whereas [Re(CO)₅Br] reacts with HSpy and (Sepy)₂ with formation of [Re(CO)₃(HSpy)₃]Br and [Re₂(CO)₆(Sepy)₂], respectively. All reactions were performed without the addition of a supporting base and the sulfur‐containing organic ligands are coordinated in their thione forms with the exception of Smetetraz^– in its μS‐bridging coordination mode in (NEt₄)[Re₂(CO)₆(μ‐S‐Smetetraz‐κS)(μ‐N,S‐Smetetraz‐κS,N)₂], which can be regarded as thiolate. The bonding mode of the selenium containing ligands in the dimeric compound [Re₂(CO)₆(Sepy)₂] (C–Se distance: 1.93 Å) can also best be described as selenolate. The products are stable on air at an ambient temperature. They were studied spectroscopically and by X‐ray diffraction.     

Synthesis,Characterization and Reactivity of the Tricarbonyl(formylcycloheptatrienyl)iron‐Anion [(η3‐C7H6CHO)Fe(CO)3]−

Deprotonation of the readily available organometallic aldehyde derivative [(η⁴‐C₇H₇CHO)Fe(CO)₃] ( 2 ) with NaN(SiMe₃)₂ in benzene solution at ambient temperature afforded the anionic formylcycloheptatrienyl complex Na[(η³‐C₇H₆CHO)Fe(CO)₃] ( 3 ). The anion is fluxional in solution and displays a unique ambident reactivity towards electrophiles (MeI, Me₃SiCl). New substituted [(η⁴‐RC₇H₆CHO)Fe(CO)₃] and [(η⁴‐heptafulvene)Fe(CO)₃] complexes have been identified as the products. Treatment of 3 with 0.5 equivalents of dimeric [(COD)RhCl]₂ (COD = 1,5‐cyclooctadiene) afforded the functionalized Fe‐Rh cycloheptatrienyl complex [(μ‐C₇H₆CHO)(CO)₃FeRh(COD)] ( 7 ) in up to 86 % yield. Carbonylation of 7 under an atmosphere of CO led to facile conversion to the heterobimetallic pentacarbonyl derivative [(μ‐C₇H₆CHO)(CO)₃FeRh(CO)₂] ( 8 ), which is also accessible in lower yield from the direct reaction of 3 with [Rh(CO)₂Cl]₂.     

Structural Systematics for Lanthanide(III) Systems: Lattice Interactions in Salts [CoL3][Ln(dipic)3]·nH2O (L = N,N′‐Aromatic Bidentate Ligand; dipic = Dipicolinate = pyridine‐2,6‐dicarboxylate) Containing Complex Ions of D3 Symmetry

Structural characterisation of a number of hydrated solids containing chiral, kinetically inert [Co(A–A)₃]³⁺ cations (A–A = 2,2′‐bipyridine, 1,10‐phenanthroline, 4,4′‐dimethyl‐2,2′‐bipyridine) and chiral, kinetically labile [Ln(dipic)₃]^3– anions (Ln = La, Eu, Tb, Ho, Er, Lu, Y, though not for all cobalt cations; dipic = dipicolinate = pyridine‐2,6‐dicarboxylate) show a remarkable range of associations between the lattice components, though all are racemic arrays. Analysis of the structures in terms of short interatomic contacts between the components shows that, whereas numerous contacts of the heteroaromatic ligands do occur, very few define an arrangement which could be truly termed “π‐stacking” where the rings are closely parallel and atom overlaps in projection are substantial. Water is important in the highly hydrated lattice structures, not only because of hydrogen‐bonding interactions with itself and carboxylate‐O atoms but also because of its interactions with the aromatic units. The family [Co(bipy)₃][Ln(dipic)₃]·~13H₂O are essentially isomorphous for the full range of Ln plus Y (triclinic, Pbar{1} , a = 12.3, b = 14.3, c = 16.5 Å, α = 94, β = 94, γ = 108 ?, Z = 2). Among the heavier lanthanides, the potential symmetry of the anion/cation combination is realised in the trigonal space group Pbar{3} , both species lying together as an ion‐pair, disposed on the trigonal axis for [Co(phen)₃][Ln(dipic)₃]·22H₂O (Ln = Eu, Er; a = 15.2, c = 16.8 Å, Z = 2).     

Synthesis and X‐Ray Single Crystal Structure of Two New Copper Complexes with the Redox Active Ligand 1,10‐Phenanthroline‐5,6‐dione

The synthesis and the crystal structures of the complexes [Cu(L^I)₂](ClO₄) ( 1 ) and [Cu(L^I)(CH₃CN)₂(ClO₄)₂] ( 2 ) are reported. 1 crystallizes in the monoclinic space group C2/c with the unit cell dimensions a = 13.169(4), b = 12.289(3), c = 14.732(3) Å, β = 109.03(2)° and Z = 4. Copper(I) is coordinated to four N atoms of the two 1,10‐Phenanthroline‐5,6‐dione (L^I) ligands with a two‐fold axis passing between the ligands. The copper(II) compound 2 crystallizes in the orthorhombic space group Pbn2₁ with unit cell dimensions of a = 7.498(5), b = 23.492(7), c = 12.363(4) Å and Z = 4. Copper(II) coordination can be described as a distorted octahedron with the N donor atoms of one L^I ligand and of two molecules of CH₃CN occupying the equatorial positions completed by two oxygen atoms of the two perchlorate molecules in the axial positions.     

Synthesis and Characterization of Diorganotin(IV) Complexes Bearing Binary Schiff‐Bases and Crystal Structure of nBu2SnL1

Four novel diorganotin(IV) complexes with general formula R₂SnL (R = nBu, PhCH₂) were synthesized from diorganotin dichlorides and binary Schiff‐bases (H₂L) containing N₂O₂ donor atoms in the presence of sodium ethoxide. The Schiff bases were prepared by reactions of o‐phenylenediamine with 3‐tert‐butyl‐2‐hydroxy‐5‐methylbenzaldehyde (H₂L¹) and salicylaldehyde (H₂L²) respectively. The compounds were characterized by elemental analyses, IR, and NMR spectroscopy. The solid‐state crystal structure of the compound nBu₂SnL¹ was determined by single‐crystal structural analysis.     

Synthesis,Structural Characterization,and Catalytic Activity of Scandium,Samarium, and Dysprosium Complexes Supported by Tris(pyrrolyl‐α‐methyl)amine Ligand

The synthesis, structures and catalytic activities of three organolanthanide complexes supported by the H₃tpa ligand (H₃tpa = tris(pyrrolyl‐α‐methyl) amine) are described. Treatment of H₃tpa with one equivalent of Ln[N(SiMe₃)₂]₃ (Ln = Sc, Sm, Dy) in THF gives, after recrystallization from toluene/THF solution, Sc(tpa)(THF)₂ ( 1 ), Sm(tpa)(THF)₃ ( 2 ) and Dy(tpa)(THF)₃ ( 3 ) in good yields. The structures of complexes 1 – 3 were determined by single‐crystal X‐ray diffraction and elemental analysis. Complexes 2 and 3 exhibited good catalytic activity for the polymerization of ?‐caprolactone.     

Synthesis and X‐ray single‐crystal structure study of 5,5′‐bis(silyl)‐functionalized 3,3′‐dibromo‐2,2′‐dithiophenes

A high‐yield synthesis toward 5,5′‐bis(silyl)‐functionalized 3,3′‐dibromo‐2,2′‐dithiophenes with very efficient work‐up procedure is presented. The molecular structures of two silyl functionalized dibromo‐dithiophenes in the solid state have been determined to investigate the structural influences of different functional groups on the degree of π‐conjugation within the dithiophene moieties, as well as their packing properties. The planar alignment of the tert‐butyldimethylsilyl‐functionalized dibromo‐dithiophene shows a significantly higher degree of conjugation of the π‐system with a more favorable molecular packing than the skewed arrangement of the triisopropylsilyl‐substituted species. Copyright © 2005 John Wiley & Sons, Ltd.     

钇与亚胺基二乙酸配合物的合成及晶体结构

合成了钇与亚胺基二乙酸的配合物，用Ｘ射线衍射法测定了配合物的单晶结构，化学式为［Ｙ２｛Ｈ２Ｎ（ＣＨ２ＣＯＯ）２｝（Ｈ２Ｏ）４］（ＣｌＯ４）２·１．２５Ｈ２Ｏ。晶体属三斜晶系，Ｐ１↑－空间群。晶胞参数：ａ＝０．９２５４（１）ｎｍ，ｂ＝０．９９２２（１）ｎｍ，ｃ＝１．０６５８（２）ｎｍ，α＝７１．４８１（１０）°，β＝７７．９５０（１０）°，γ＝６５．３５０（１０）°，Ｖ＝０．８４０１（２）＾３，Ｚ＝     

Crystal Structure and Characterization of Pd(II) Bis(diiso‐propyldithiocarbamate) Complex

The crystal and molecular structure of [Pd(iPr₂dtc)₂] (dtc = dithiocarbamate) have been determined by X‐ray crystallography. The unit cell of the crystal structure consists of two discrete monomelic molecules of [Pd(iPr₂dtc)₂]. The Pd(II) ion has an square‐planar geometry. The electronic and IR spectral data are in agreement with the X‐ray structure. The TG data indicate slight degradation of a few percent.     

Synthesis and Characterization of the First Bisand Tris[1‐(ω‐alken‐1‐yl)indenyl]lanthanide Complexes

1‐Allyl‐2,4,7‐trimethyl‐1 H‐indene ( 1 ) and 1‐(3‐buten‐1‐yl)‐4,7‐dimethyl‐1 H‐indene ( 2 ), which are to prepare from (2,4,7‐trimethylindenyl)lithium and allyl chloride or from (4,7‐dimethylindenyl)lithium and 4‐bromo‐1‐butene, react with n‐butyllithium yielding (1‐allyl‐2,4,7‐trimethylindenyl)lithium [LiL ( 1 a )] or [1‐(3‐buten‐1‐yl)‐4,7‐dimethylindenyl]lithium [LiL′ ( 2 a )], respectively. The reactions of the trichlorides of gadolinium, erbium, yttrium, lutetium, and ytterbium with 1 a or 2 a (mole ratio 1 : 2) in THF produce the bis(indenyl)lanthanide chloride complexes L₂LnCl(THF) [Ln = Gd ( 1 b ), Er ( 1 c )], LLnCl(THF) [Y ( 2 d ), Lu ( 2 e )], or LYb(μ‐Cl)₂Li(THF)₂ ( 2 f ), whereas the trichlorides of the comparatively large samarium and lanthanum ions react with different molar amounts of 2 a in THF exclusively with formation of the tris(indenyl) complexes LSm ( 2 g ) or LLa(μ‐Cl)Li(Et₂O)₃ ( 2 h ), respectively. All new compounds were characterized by elemental analyses, mass spectrometry, and the diamagnetic compounds 2 d , 2 e and 2 h also by ¹H and ¹³C{¹H}‐NMR spectroscopy. The single crystal X‐ray structural analyses of 1 c , 2 f , 2 g and 2 h demonstrate that the alkenyl groups of the indenyl side chains are not coordinated to the lanthanide atoms.