New substituted titanocene, zirconocene and hafnocene dichlorides

Summary Twentytwo new substituted metallocene Cp¹Cp²MCl₂ (M = Ti, Zr or Hf) dichlorides have been prepared and the catalytic activity of some of them in alkene polymerization has been primarily evaluated.     

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph₂P‐N‐PPh₂ at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp₂TiCl)₂] (Cp=η⁵‐cyclopentadienyl) generated [Cp₂Ti(Cl)P(Ph₂)N(H)PPh₂] ( 2 ). The heterometallacyclic complex [Cp₂Ti(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp₂Ti(η²‐Me₃SiC₂SiMe₃)] with the amine 1 . Reactions of the lithium amide [(thf)₃Li{N(PPh₂)₂}] with [Cp₂MCl₂] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp₂M(Cl){κ²‐N,P‐N(PPh₂)₂}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp₂Zr(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.     

A cyclopentadienyl ring exchange method for the attachment of early transition metal metallocene dichlorides to a polymer support

PMR and mass spectral analysis have been used to study the interchange of π-bonded cyclopentadienyl rings with σ-bonded cyclopentadienyl rings in the compounds (C₅H₅)₄M (M = Ti, Zr, Hf, Nb, Ta, Mo and W) and (C₅H₅)₃V or a-bonded benzylcyclopentadienyl rings in the compounds (C₆H₅CH₂C₅H₄) (C₅H₅)₂MC1 (M = Ti, Zr, Hf, Nb, Ta, Mo and W). As soon as the Cp₄M species are generated (indicated by a color change), the interchange occurs and the equilibrium is established. As reported, no such interchange was observed in (C₅H₅) ₄Mo in the PMR time scale; however, it does occur after a longer time. By using this interchange behavior of the cyclopentadienyl ring, metallocene dichlorides of Ti, Zr, Hf, V, Nb, Ta, Mo and W have been attached to polystyrene-divinylbenzene beads.     

Reactions of Group 4 Metallocenes with Monosubstituted Acetonitriles: Keteniminate Formation versus CC Coupling

The reactions of the Group 4 metallocene dichlorides [Cp′₂MCl₂] ( 1 a : M=Ti, Cp′=Cp*=η⁵‐pentamethylcyclopentadienyl, 1 b : M=Zr, Cp′=Cp=η⁵‐cyclopentadienyl) with lithiated MesCH₂?C?N gave [Cp*₂TiCl(N=C=C(HMes))] ( 3 ; Mes=mesityl) in the case of 1 a . For compound 1 b , a nitrile–nitrile coupling resulted in a five‐membered bridge in 4 . The reaction of the metallocene alkyne complex [Cp*₂Zr(η²‐Me₃SiC₂SiMe₃)] ( 2 ) with PhCH₂?C?N led in the first step to the unstable product [Cp*₂Zr(η²‐Me₃SiC₂SiMe₃)(NC?CH₂Ph)] ( 5 ). After the elimination of the alkyne, a mixture of products was formed. By variation of the solvent and the reaction temperature, three compounds were isolated: a diazadiene complex 6 , a bis(keteniminate) complex 7 , and 8 with a keteniminate ligand and a five‐membered metallacycle. Subsequent variation of the Cp ligand and the metal center by using [Cp₂Zr] and [Cp*₂Ti] with Me₃SiC₂SiMe₃ in the reactions with PhCH₂?C?N gave complex mixtures.     

Elimination of bis(trimethylsilyl)stannylene from tris(trimethylsilyl)stannylated zirconocene and hafnocene chlorides

Reactions of (Me₃Si)₃SnK with Cp₂MCl₂ (M = Zr, Hf) give the respective stannylated metallocene chlorides. These complexes display a tendency to eliminate bis(trimethylsilyl)-stannylene under Cp₂M(Cl)SiMe₃ formation.     

Synthesis and Characterization of Multiferrocenyl‐Substituted Group 4 Metallocene Complexes

The reaction of different metallocene fragments [Cp₂M] (Cp=η⁵‐cyclopentadienyl, M=Ti, Zr) with diferrocenylacetylene and 1,4‐diferrocenylbuta‐1,3‐diyne is described. The titanocene complexes form the highly strained three‐ and five‐membered ring systems [Cp₂Ti(η²‐FcC₂Fc)] ( 1 ) and [Cp₂Ti(η⁴‐FcC₄Fc)] ( 2 ) (Fc=[Fe(η⁵‐C₅H₄)(η⁵‐C₅H₅)]) by addition of the appropriate alkyne or diyne to Cp₂Ti. Zirconocene precursors react with diferrocenyl‐ and ferrocenylphenylacetylene under C? C bond coupling to yield the metallacyclopentadienes [Cp₂Zr(C₄Fc₄)] ( 3 ) and [Cp₂Zr(C₄Fc₂Ph₂)] ( 5 ), respectively. The exchange of the zirconocene unit in 3 by hydrogen atoms opens the route to the super‐crowded ferrocenyl‐substituted compound tetraferrocenylbutadiene ( 4 ). On the other hand, the reaction of 1,4‐diferrocenylbuta‐1,3‐diyne with zirconocene complexes afforded a cleavage of the central C? C bond, and thus, dinuclear [{Cp₂Zr(μ‐η¹:η²‐C?CFc)}₂] ( 6 ) that consists of two zirconocene acetylide groups was formed. Most of the complexes were characterized by single‐crystal X‐ray crystallography, showing attractive multinuclear molecules. The redox properties of 3 , 5 , and 6 were studied by cyclic voltammetry. Upon oxidation to 3 ⁿ⁺, 5 ⁿ⁺, and 6 ⁿ⁺ (n=1–3), decomposition occured with in situ formation of new species. The follow‐up products from 3 and 5 possess two or four reversible redox events pointing to butadiene‐based molecules. However, the dinuclear complex 6 afforded ethynylferrocene under the measurement conditions.     

Catenated polysulfur ligands: the pentasulfides of di-η5-cyclopentadienyl-zirconium(IV) and -hafnium(IV)

The thiols Cp₂M(SH)₂, where M = Ti and Zr, react to form the complexes Cp₂MS₅ when treated with mono- and di-sulfur transfer reagents. Treatment of Cp₂MCl₂ with Li₂S₂ and sulfur gave Cp₂MS₅, M = Ti, Zr and Hf, in better yield. The new Zr and Hf complexes have a six-membered MS₅ ring in a chair conformation similar to the previously observed for M = Ti. Variable temperature NMR studies show that the barriers to MS₅ ring inversion decrease in the order Ti > Hf > Zr.     

Cyclic organohydroborate complexes of metallocenes: VIII. Triphenylsiloxy derivatives of Group IV organometallic systems, Cp2M(OSiPh3)X (M=Ti, Zr, Hf; X=Cl, {(μ-H)2BC8H14})

Group IV metallocene triphenylsiloxy chlorides, Cp₂MCl(OSiPh₃) (1, M=Ti; 2, M=Zr; 3, M=Hf), and cyclic organohydroborates, Cp₂M(OSiPh₃){(μ-H)₂BC₈H₁₄} (4, M=Zr; 5, M=Hf), were synthesized and characterized. The new hafnocene chloride derivative 3 was obtained by treating Cp₂HfCl₂ with triphenylsilanol and piperidine. The 18-electron cyclic organohydroborates 4 and 5 were afforded by reacting 2 and 3 with K[H₂BC₈H₁₄], the potassium salt of the 9-BBN dimer. Reaction of 1 with K[H₂BC₈H₁₄] causes reduction of the Ti(IV) center and produces the well-known Ti(III), 17-electron, paramagnetic dimer [Cp₂Ti(μ-Cl)₂TiCp₂] (6). Single-crystal X-ray diffraction structures of 3, 4, 5, and 6 were determined.     

Vinylierung und 91Zr-NMR-Spektren von Substituierten Zirconocendichloriden

Vinylation and ⁹¹Zr N.M.R. Spectra of substituted Zirconocene Dichlorides Substituted zirconocene dichlorides react with vinyl lithium with formation of zirconacyclopent-2-enes, Cp₂ZrCH = CHCH₂CH₂, or zirconocene butadiene complexes, Cp₂Zr(C₄H₆). The compounds obtained were characterized by their ¹H and ¹³C n.m.r. spectra. The ⁹¹Zr n.m.r. chemical shifts of substituted zirconocene dichlorides correlate with the bond angles Cp′? Zr? Cp′ and Cl? Zr? Cl respectively. They can be used to estimate the reaction behaviour of zirconocene dichlorides.     

Ti Group Metallocene-Catalyzed Synthesis of 1-Hexene Dimers and Tetramers

1-Hexene transformations in the catalytic systems L₂MCl₂–XAlBuⁱ₂ (L = Cp, M = Ti, Zr, Hf; L = Ind, rac-H₄C₂[THInd]₂, M = Zr; X = H, Bu ⁱ) and [Cp₂ZrH₂]₂-ClAlR₂ activated by MMAO-12, B(C₆F₅)₃, or (Ph₃C)[B(C₆F₅)₄] in chlorinated solvents (CH₂Cl₂, CHCl₃, o-Cl₂C₆H₄, ClCH₂CH₂Cl) were studied. The systems [Cp₂ZrH₂]₂-MMAO-12, [Cp₂ZrH₂]₂-ClAlBuⁱ₂-MMAO-12, or Cp₂ZrCl₂-HAlBuⁱ₂-MMAO-12 (B(C₆F₅)₃) in CH₂Cl₂ showed the highest activity and selectivity towards the formation of vinylidene head-to-tail alkene dimers. The use of chloroform as a solvent provides further in situ dimer dimerization to give a tetramer yield of up to 89%. A study of the reaction of [Cp₂ZrH₂]₂ or Cp₂ZrCl₂ with organoaluminum compounds and MMAO-12 by NMR spectroscopy confirmed the formation of Zr,Zr-hydride clusters as key intermediates of the alkene dimerization. The probable structure of the Zr,Zr-hydride clusters and ways of their generation in the catalytic systems were analyzed using a quantum chemical approach (DFT).     

Access a divers dichalcogenophenylenes metallocenes (M = Ti, Zr, Hf). Premier exemple d'un ditellurophenylene-zirconocene

Elementary sulfur and selenium combine (in boiling heptane) with [(tBuCp)₂-Zr(C₆H₄R)₂] (Cp = η⁵-C₅H₄; R = OCH₃) to give the corresponding dichalcogenophenylenezirconocene. With tellurium, the reaction proceeds only at lower temperature (in boiling hexane), affording the first ditellurophenylenezirconocene. As no metallacycle was obtained with the Cp ligand or when the metal is Hf, complexes of the general type [(RCp)₂MSe₂C₆H₄-o] (M = Ti, Zr, Hf; R = H, t-Bu, (CH₃)₅) have been synthesized by allowing metallocene dichlorides to react with potassium benzenediselenolate, prepared by cleaving [(t-BuCp)₂ZrSe₂C₆H₄-o] with t-BuOK.     

Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands

A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp₂M(Cl){κ²‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp₂MCl₂] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp₂Zr(H)Cl]. Salt metathesis reaction of [Cp₂Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp₂M(H){κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)₃Mg(Cl) {κ²‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′₂Ti{κ²‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp₂′Ti(η²‐Me₃SiC₂SiMe₃)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy.     

A proposal on an index of activities and selectivities of olefin polymerization catalysts by using 'paired interacting orbitals (PIO)' analysis

Olefin insertion and chain transfer to monomer on [O_h-CH₃MCl₄]^m(M = Ti, Zr, m = –1, –2: models of Ziegler-Natta catalysts) and [T_d-CH₃ML₂]^m(M = Ti, Zr; L = Cl, Cp m = 0, +1: models of metallocene catalysts) were analyzed by paired interacting orbitals (PIO) proposed by Fujimoto et al. Polymerization activities, molecular weights and regioselectivities of propylene insertion were easily predicted by using the total overlap population of all PIOs as an index of catalytic reactions.     

Edge-shared [M2Cl10]2? complexes of reaction between oxophilic group 4 metal and phosphorus ylides

The reactions between oxophilic group 4 metal chlorides, ??-keto ylides in THF, led to the formation of titanium, zirconium and hafnium edge-shared [M₂Cl₁₀]^2? complexes (1a?C3f). We describe that the reaction between MCl₄ (M = Ti, Zr and Hf) with phosphorus ylides produce edge-shared [M₂X₁₀]^2? complexes instead of O-coordination previously reported complexes. Adding dimethyl sulfoxide (DMSO) to these complexes in room temperature crystalline solid [M(DMSO)₈] · 4Cl · mH₂O · DMSO] (M = Ti (1g), Zr (2g) and Hf (3g); m = 0?C3) together with phosphonium salts in mother liquid were formed. The compounds were characterized by elemental analysis, IR and ¹H, ¹³C and ³¹P NMR spectroscopy.     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.     

Advantages of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes as Metallocene Sources Towards Other Synthetically used Systems

Active species for synthetic and catalytic applications are formed from well defined complexes or mixtures of compounds. For group 4 metallocenes, three pathways for the formation of the reactive complex fragment [Cp′₂M] are known: (i) reductive mixtures and well defined complexes which are able to form the metallocene fragments either by (ii) addition or (iii) substitution reactions. In this account for each of theses systems (i)–(iii) a prominent example will be discussed in detail, (i) the Negishi reagent Cp₂ZrCl₂/n-BuLi, (ii) bis(η⁵ : η¹-pentafulvene) complexes and (iii) metallocene bis(trimethylsilyl)acetylene complexes, to show the advantages and the disadvantages for each of these methods for synthetic applications. This account summarizes some main advantages of group 4 metallocene bis(trimethylsilyl)acetylene complexes as metallocene generating agents over other synthetically used systems. For each of the special purposes, all described systems have advantages as well as disadvantages. The aim of this overview is to help synthetic chemists in selecting the most effective system on the basis of [Cp′₂M] (M=Ti, Zr) for synthetic or catalytic puposes.     

Cycloaddition of tertiary amines to fullerene C<Subscript>60</Subscript>, catalyzed by Ti,Zr, and Hf complexes

Cycloaddition of various tertiary amines to fullerene C₆₀ in the presence of Cp₂MCl₂ complexes (M = Ti, Zr, Hf) in toluene at 20–150°C in 3–48 h leads to the formation of pyrrolofullerenes in high yields.     

Reactions of the metallocene dichlorides [M(Cp)2Cl2] (M = Zr, Hf) and [Ti(MeCp)2Cl2] with the pyridine-2,6-dicarboxylate(−2) ligand: Synthesis, spectroscopic characterization and X-ray structures of the products

The reactivity pattern of the 16-electron species [M(Cp)₂Cl₂] (M = Zr, Hf; Cp⁻ = η⁵-C₅H₅⁻) and [Ti(MeCp)₂Cl₂] (MeCp⁻ = η⁵-C₅H₄CH₃⁻) towards the dipicolinate(−2) (dipic²⁻) ligand under mild (ambient temperature) and convenient (aerobic reactions, aqueous media) conditions have been investigated. The syntheses, molecular structures and spectroscopic (IR, ¹H NMR) characterization are reported for the 18-electron products [Zr(Cp)₂(dipic)] (1), [Hf(Cp)₂(dipic)] (2) and [Ti(MeCp)₂(dipic)] (3). The dipic²⁻ ion behaves as N,O,O′-chelating ligand in the three complexes, while the centroids of the Cp⁻ (1, 2) and MeCp⁻ (3) rings formally occupy the fourth and fifth coordination sites about the central metal. The two identical/very similar bite angles of only ∼70° make the dipic²⁻ ligand particularly suited to form stable metallocene derivatives with 5-coordinate geometry. IR and ¹H NMR data are discussed in terms of the known structures and the tridentate chelating mode of the dipic²⁻ ligand.     

Synthesis,characterization and toxicity of new heterobimetallic complexes of platinum(II) and palladium(II)

Heterobimetallic complexes of the type [M(C₆H₆N₂)₂(M′)₂(R)₄]Cl₂ have been synthesized by the direct reaction of [M(C₆H₈N₂)₂]Cl₂ with Group 4 or 14 organometallic dichlorides Ph₂M′Cl₂,Me₂M′Cl₂ or Cp₂M″Cl₂ in 1:2 molar ratio in MeOH (M = Pd or Pt, M′ = Si or Sn and M″ = Ti or Zr). The compounds were characterized by elemental analysis, molecular weight determination, electronic, ¹H NMR and IR spectra, magnetic susceptibilities and conductivity measurements. These studies showed that the compounds are monomers and dimagnetic in nature, with a square‐planar geometry around palladium and platinum metals. Both the free ligands and their metal complexes were screened for antimicrobial activity on different species of pathogenic fungi and bacteria and were found active in this respect.Copyright © 2001 John Wiley & Sons, Ltd.     

Synthese und Charakterisierung von Metallocen-Chelaten heterocyclischer 1,2-Dithiolate

Synthesis and Characterization of Metallocene Chelates of Heterocyclic 1,2-Dithiolates Synthesis and properties of metalocene dithiolene chelates Cp₂ML with metal(IV) ions (M) of group IVA (Ti, Zr, Hf) and of vanadium with L = dmit (1,3-dithiole-2-thione-4,5-dithiolate), dmt (1,2-dithiole-3-thione-4,5-dithiolate), dmid (1,3-dithiole-2-one-4,5-dithiolate) and dmise (1,3-dithiole-2-selone-4,5-dithiolate) are described. The structures of these compounds were discussed using IR-, UV/VIS-, ¹H-NMR-, ¹³C-NMR- and EPR data. The activation parameters of the chelate ring inversion of titanocene dithiolenes (Cp₂TiL) and the x-ray structure of Cp₂Ti(dmid) are given.