Homo- and hetero-binuclear ansa-metallocenes of the group 4 transition metals as homogeneous co-catalysts for the polymerisation of ethene and propene

The compounds [M{(CH₂)₄C(η-C₅H₄)₂}(η-C₅H₅)Cl] (M=Zr^*, Hf), [M{(CH₂)₄C(η-C₅H₄)₂}(η-C₅H₅)Me] (M=Zr, Hf), [(η-C₅H₅)MCl₂{(CH₂)₄C(η-C₅H₄)₂}MCl₂(η-C₅H₅)] (M=Zr, Hf), [(η-C₅H₅)ZrCl₂{(CH₂)₄C(η-C₅H₄)(η-C₉H₆)}ZrCl₂(η-C₅H₅)], [(η-C₅H₅)MMe₂{(CH₂)₄C(η-C₅H₄)₂}MMe₂(η-C₅H₅)] (M=Zr, Hf), [(η-C₅H₅)ZrCl₂{(CH₂)₄C(η-C₅H₄)₂}HfCl₂(η-C₅H₅)], [(η-C₅H₅)MCl₂{(CH₂)₄C(η-C₅H₄)₂}Rh(η-C₈H₁₂)] (M=Zr^*, Hf), [(η-C₅H₅)ZrCl₂{(CH₂)₄C(η-C₅H₄)₂}TiCl₃], [(η-C₅H₅)ZrMe₂{(CH₂)₄C(η-C₅H₄)₂}HfMe₂(η-C₅H₅)], [(η-C₅H₅)MMe₂{(CH₂)₄C(η-C₅H₄)₂}Rh(η-C₈H₁₂)] (M=Zr^*, Hf) have been prepared and characterised. ^* indicates the crystal structure has been determined. Their catalytic properties for ethene and propene polymerisation have been explored.     

Chlorures de mono- et dialkyl-zirconocene et-hafnocene

Condensation of cyclopentadienyl anions obtained from fulvenes and tetra- chloride metal to prepare (η⁵-RC₅H₄)₂MCl₂, R = alkyl; M = Zr or Hf is described. The prochiral complexes (η⁵-RC₅H₄) (η⁵-C₅H₅)MCl₂ are prepared in a similar way from MCl₄ (M = Zr), but the best method uses (η⁵-C₅H₅)ZrCl₃ or (η⁵-C₅H₅)HfCl₃, 2THF. Preparation of this adduct is described.     

C2-Bridged sandwich and half-sandwich entities with Ti(IV) and Cr(0) centers

The intense purple colored bi- and trimetallic complexes {Ti}(CH₂SiMe₃)[CC(η⁶-C₆H₅)Cr(CO)₃] (3) ({Ti}=(η⁵-C₅H₅)₂Ti) and [Ti][CC(η⁶-C₆H₅)Cr(CO)₃]₂ (5) {[Ti]=(η⁵-C₅H₄SiMe₃)₂Ti}, in which next to a Ti(IV) center a Cr(0) atom is present, are accessible by the reaction of Li[CC(η⁶-C₆H₅)Cr(CO)₃] (2) with {Ti}(CH₂SiMe₃)Cl (1) or [Ti]Cl₂ (4) in a 1:1 or 2:1 molar ratio. The chemical and electrochemical properties of 3, 5, {Ti}(CH₂SiMe₃)(CCFc) [Fc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄)] and [Ti][(CC)_nMc][(CC)_mM′c] [n, m=1, 2; n=m; n≠m; Mc=(η⁵-C₅H₅)Fe(η⁵-C₅H₄); M′c=(η⁵-C₅H₅)Ru(η⁵-C₅H₄); Mc=M′c; Mc≠M′c] will be comparatively discussed.     

Oxo-titanium and -zirconium diphosphines [(η-C5H5)2M(CH2PPh2]2O (with M = Ti,Az) as building blocks for heterobimetallic complexes

Oxo-titanium and -zirconium diphosphines [(η-C₅H₅)₂M(CH₂PPh₂)]₂ (with M = Ti, Zr) were synthesized and treated with [Rh(CO)₂Cl]₂ to give the heterobimetallic d⁰-d⁸ species O[(η-C₅H₅)₂M(CH₂PPh₂)]₂Rh(CO)Cl.     

Pyrolysis of metallocene complexes (ηC5H4R)2MR: An organometallic route to metal carbide (MC) materials (M = Ti,Zr, Hf)

The following compounds were prepared and their pyrolysis in a stream of argon was studied: (η⁵-C₅H₅)₂Ti(C?CC₆H₅)₂, (η⁵-C₅H₄SiMe₃)₂-Ti(SH)₂, [(η⁵-C₅H₅)Ti(μ-CH₂)]₂, (η⁵-C₅H₅)₂ZrR₂-(R?CH₂, CH₂C₆H₅, N(CH₃)₂), (η⁵-C₅H₄CH₃)₂-Zr(C?CC₆H₅)₂, [(η⁵-C₅H₄SiMe₃)₂Zr(μ-S)]₂, [(η⁵-C₅H₄SiMe₃)₂Hf(μ-S)]₂ and (η⁵-C₅H₄SiMe₃)₂Hf-(C?CC₆H₅)₂. The products of bulk pyrolysis of these materials were formed in 20–40% yield, based on the charged sample weight, and consisted mainly of titanium carbide together with small amounts of amorphous carbon.     

Complexes du titane et du zirconium contenant les ligands cyclopentadienyldiphenylphosphine et cyclopentadienylethyldiphenylphosphine: acces a des structures heterobimetalliques

Reactions of Ph₂P(CH₂)_n(C₅H₄)Li, (n = 0, 2), with MCl₄ or CpTiCl₃ (M = Ti, Zr; Cp = η⁵-C₅H₅) form Cl₂M[(η⁵-C₅H₄)(CH₂)_nPPh₂]₂ or Cl₂CpTi[(η⁵-C₅H₄)-(CH₂)₂PPh₂] in good yields. Chemical reduction with Al, or electrochemical reduction of these complexes, under CO, are described. The titanium(IV) and zirconium(IV) derivatives react with metal carbonyls (Mo(CO)₆, Cr(CO)₆, Fe(CO)₅, Mo(CO)₄(C₈H₁₂)) under formation of new heterobimetallic complexes. Reduction with Al of Cl₂CpTi[(η⁵-C₅H₄)(CH₂)₂PPh₂]Mo(CO)₅ under CO results in a new heterobimetallic species containing low valent titanium. Both complexes Cl₂M[(η⁵-C₅H₄)(CH₂)₂PPh₂]₂ (M = Ti, Zr) react with [Rh(μ-Cl)(CO)(C₂H₄)]₂ to yield {RhCl(CO)(Cl₂M[(η⁵-C₅H₄)(CH₂)₂PPh₂]₂)}x, which is assumed to be a dimer, in which the titanium or the zirconium compounds act as bridging diphosphine ligands between the rhodium atoms.     

Preparation of new (η5-C5H4CH3)Mn(NO)(PPh3) and (η7-C7H7)Mo(CO)-(PPh3) complexes

The complex (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)I has been prepared by the reaction of NaI with [(η⁵-C₅H₄CH₃)Mn(NO)(CO)(PPh₃)]⁺ and also by the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI followed by PPh₃. This iodide compound reacts with NaCN to yield (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CNC₂H₅)]⁺. Both [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ and [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CO)]⁺ react with NaCN to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂]^?. This anion reacts with Ph₃SnCl to yield cis-(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂SnPh₃ and with [(C₂-H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CNC₂H₅)₂]⁺. The reaction of (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I with AgBF₄ in acetonitrile yields [(η⁵-C₅H₄CH₃)Mn-(NO)(PPh₃)(NCCH₃)]⁺. The complex (η⁵-C₅H₄CH₃)Mn(NO)(CO)I, produced in the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI, is not stable and decomposes to the dimeric complex (η⁵-C₅H₄CH₃)₂Mn₂(NO)₃I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η⁷-C₇H₇)Mo(CO)(PPh₃)I with NaCN yields (η⁷-C₇-H₇)Mo(CO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁷-C₇H₇)-Mo(CO)(PPh₃)(CNC₂H₅)]⁺. The interaction of this molybdenum halide complex with AgBF₄ in acetonitrile and pyridine yields [(η⁷-C₇H₇)Mo(CO)(PPh₃)-(NCCH₃)]⁺ and [(η⁷-C₇H₇)Mo(CO)(PPh₃)(NC₅H₅)]⁺, respectively. Both (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I and (η⁷-C₇H₇)Mo(CO)(PPh₃)I are oxidized by NOPF₆ to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data.     

The synthesis and characterization of metal-containing vinylic monomers of iron and tungsten

A series of metal-containing vinylic monomers of the type L_nM(COC₆H₄CH=CH₂) and L_nM (COCH=CHC₆H₅) [L_nM = (η⁵-C₅H₅)Fe(CO)₂, (η⁵-C₅Me₅)Fe(CO)₂ and (η⁵-C₅H₅)W(CO)₃] were prepared by the reaction of the appropriate metal anion with either 4-vinylbenzoyl chloride or cinnamoyl chloride. (η⁵-C₅H₅)(CO)₂FeCOCH=CH₂ was prepared by the reaction of Na[(η⁵-C₅H₅)Fe(CO)₂] and acryloyl chloride, whereas the compound (η⁵-C₅H₅)(CO)₂Fe(C₆H₄CH=CH₂) was prepared via a transmetallation reaction using a palladium catalyst. All compounds were fully characterized using FTIR, ¹H and ¹³C NMR spectroscopy and mass spectrometry. Copyright © 1998 John Wiley & Sons, Ltd.     

Use of an optically active germanium species for the resolution of diastereoisomeric transition metal complexes with five different and independent ligands

Reaction of optically active MePh(1-C₁₀H₇)GeLi with (η⁵-C₅H₅)M(CO)₂NO (M = Mo, W) results in replacement of CO and formation of anionic species which can be alkylated with CH₃I to afford mixtures of diastereoisomeric complexes, (η⁵-C₅H₅)M(CO)(NO)(GeR₃)CH₃ (R₃ = MePh(1-C₁₀H₇); M = Mo, W). These complexes are the first in which a transition metal, surrounded by five different ligands shows optical activity. These compounds are not fluxional and show a high optical stability; under forcing conditions decomposition occurs before epimerisation.     

Photo-degradation studies on di-η5-cyclopentadienyl-dimethyltantalum and some deuterated analogs

The synthesis of (η⁵-C₅H₅)₂Ta(CH₃)₂ in 61% yield from (η⁵-C₅H₅)₂TaCl₂ and methyllithium is described. Photo-degradation of (η⁵-C₅H₅)₂Ta(CH₃)₂ in hydrocarbon solvents results in cleavage of the carbon—tantalum sigma bond. Methane is the major gaseous photo-product. Similar results are obtained in the thermolysis of (η⁵-C₅H₅)₂Ta(CH₃)₂. Deuterium labelling studies indicate that the methyl ligands, the cyclopentadienyl rings and the solvent are all sources of hydrogen in the photochemically-induced formation of methane. The extent to which each source is active in this process cannot be determined, due to an isotopic preference of hydrogen over deuterium. (η⁵-C₅H₅)₂Ta(CH₃)₃ and (C₁₀H₁₀Ta)_x are isolated from the photolysis of (η⁵-C₅H₅)₂Ta(CH₃)₂ in pentane. Irradiation of (η⁵-C₅H₅)₂Ta(CH₃)₂ in the presence of carbon monoxide results in formation of (η⁵-C₅H₅)₂Ta(CO)CH₃.     

Exploratory organometal-sulfur chemistry; syntheses and unusual properties of rhenium CH2SR,CHSRR′, and CHSR]+ complexes

The methylidene complex [(η-C₅H₅)Re(NO)(PPh₃)(CH₂)]⁺PF₆^?(I) yields kinetically labile sulfonium salts when treated with CH₃SCH₃, CH₃SCH₂C₆H₅, and (η-C₅H₅)Re(NO)(PPh₃)(CH₂SCH₃) (V);the binuclear adduct formed in the latter case, [(η-C₅H₅)Re(NO)(PPh₃)CH₂]₂S⁺CH₃ (VI), is substantially more stable than the others and undergoes hydride transfer disproportionation to [(η-C₅H₅)Re(NO)(PPh₃)(CHSCH₃)]⁺PF₆^?(VII) and (η-C₅H₅)Re(NO)(PPh₃)(CH₃) (VIII) when heated.     

Photo-degradation studies on Di-η5-Cyclopentadienyldimethylvanadium,Di-η5-Cyclopentadienylmethylvanadium,Di-η5-Cyclopentadienyldimethylniobium,and some deuterated analogs

The photolysis of alkyl metallocene derivatives of vanadium and niobium in hydrocarbon solvents results in cleavage of the carbon—metal σ-bond. In the cases of (η⁵-C₅H₅)₂VCH₃ and (η⁵-C₅H₅)₂Nb(CH₃)₂, only methane (>99%) is produced photochemically. (η⁵-C₅H₅)₂V(CH₃)₂, prepared on a convenient new synthesis from (η⁵-C₅H₅)₂VCl₂ and methyllithium in toluene, degrades under photochemical conditions to yield both methane and ethane in a 2 : 1 ratio. The ethane arises from intra- and intermolecular methyl dimerization. Deuterium labeling studies have shown that the methyl group, the cyclopentadienyl ring, and the solvent are all sources of hydrogen in the formation of methane in these photolyses. The extent to which each source participates in the hydrogen abstraction process cannot be quantitatively determined because of the influence of an isotope effect. Chemical reactions with carbon monoxide during the photolyses give low yields of (η⁵-C₅H₅)V(CO)₄ from (η⁵-C₅H₅)₂VCH₃ or (η⁵-C₅H₅)₂V(CH₃)₂, and of (η⁵-C₅H₅)₂Nb(CO)CH₃ from (η⁵-C₅H₅)₂Nb(CH₃)₂.     

Amidoamine-based dendrimers with end-grafted Pd-Fe units: Synthesis, characterization and their use in the Heck reaction

The synthesis and characterization of novel amidoamine-based metallodendrimers with heterobimetallic end-grafted amidoferrocenyl-palladium-allyl chloride units is described. Dendrimer (Fe((η⁵-C₅H₄PPh₂)(η⁵-C₅H₄))C(O)HNCH₂CH₂NHC(O)CH₂CH₂)N[CH₂CH₂N(CH₂CH₂C(O)NHCH₂CH₂NH-C(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂)))₂]₂ (9-Fe) and the corresponding metal species (Fe((η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))(η⁵-C₅H₄))C(O)HNCH₂CH₂NHC(O)CH₂CH₂)N[CH₂CH₂N(CH₂CH₂C(O)NHCH₂CH₂NHC(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))))₂]₂ (9-Fe-Pd) were prepared by a consecutive divergent synthesis methodology including addition-amidation cycles, standard peptide coupling, and coordination procedures. For comparative reasons also the monomeric and dimeric molecules (Fe(η⁵-C₅H₄PPh₂)(η⁵-C₅H₄C(O)NHⁿC₃H₇)) (5-Fe) and [Fe(η⁵-C₅H₄PPh₂)(η⁵-C₅H₄C(O)NHCH₂)]₂ (6-Fe) as well as N(CH₂CH₂C(O)NHCH₂CH₂NHC(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂)))₃ (7-Fe) and [CH₂N(CH₂CH₂C(O)NHCH₂CH₂NHC(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂)))₂]₂ (8-Fe) were prepared from Fe(η⁵-C₅H₄PPh₂)(η⁵-C₅H₄CO₂H) (3). Using [Pd(η³-C₃H₅)Cl]₂ (4) as palladium source heterobimetallic metallodendrimers (Fe(η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))(η⁵-C₅H₄C(O)NHⁿC₃H₇)) (5-Fe-Pd), [Fe(η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))(η⁵-C₅H₄C(O)NHCH₂)]₂ (6-Fe-Pd), N(CH₂CH₂C(O)NHCH₂CH₂NHC(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))))₃ (7-Fe-Pd) and [CH₂N(CH₂CH₂C(O)NHCH₂CH₂NHC(O)(Fe(η⁵-C₅H₄)(η⁵-C₅H₄PPh₂(Pd(η³-C₃H₅)Cl))))₂]₂ (8-Fe-Pd) were synthesized. Additionally, seleno-phosphines of 5-Fe-Se and 9-Fe-Se, respectively, were prepared by addition of elemental selenium to 5-Fe or 9-Fe to estimate their σ-donor properties.The palladium-containing amidoamine supports are catalytically active in the Heck-Mizoroki cross-coupling of iodobenzene with tert-butyl acrylate. The catalytic data are compared to those obtained for the appropriate mononuclear and dinuclear compounds 5-Fe-Pd and 6-Fe-Pd. This comparison confirms a positive cooperative effect. The mercury drop test showed that (nano)particles were formed during catalysis, following on heterogeneous carbon-carbon cross-coupling.     

Inorganic Polymers : by N.H. Ray,Academic Press,New York/San Francisco/London, 1978, 174 pages, $ 17.35.

Insertion of CO or p-TolNC into a ZrC bond of [Zr(η-C₅H₅).(R)R′] under ambient conditions in C₆H₆ leads to the stable η²-acyl- or η²-iminoacyl-complex [Zr(η-C₅H₅)₂{η²-C(X)R}R′] (X = O or NTol-p); with [Zr(η-C₅H₅)₂{CH(SiMe₃)₂}Me] as substrate there is exclusive preference for scission of the more hindered ZrC bond.     

Synthesis of hetero-binuclear derivatives of the tetrathiolato complexes [Mo(η-C5H5CH2SR)2)], R = Prn and Ph,with platinum,palladium, and rhodium

The compound Mo(η-C₅H₄(CH₂)₂SPrⁿ)₂(SPrⁿ)₂ acts as a bidentate ligand giving the heteronuclear bi-metallic compounds [Mo(η-C₅H₄CH₂CH₂SPrⁿ)₂-(SPrⁿ)₂(PtCl₂)],[Mo(η-C₅H₄CH₂CH₂SPrⁿ)₂(SPrⁿ)₂(PdCl₂)₂], [Mo(η-C₅C₄CH₂CH₂SPrⁿ)₂(SPrⁿ)₂(RhCl₃)₂], [Mo(η-C₅H₄CH₂CH2SPrⁿ)₂(μ-SPrⁿ)₂Rh(dppe)]BF₄, [Mo(η-C₅H₄CH₂CH₂SPrⁿ)₂(μ-SPrⁿ)₂(COD)Rh]Cl, [Mo(η-C₅H₄CH₂CH₂SPrⁿ)₂-(μ-SPrⁿ)₂Pt(PPh₃)₂](PF₆)₂, and the compound [Mo(η-C₅H₄(CH₂)₂-μ-SPh)₂Cl₂Rh(COD)]Cl bonds via the ring-sulphur substituents giving [Mo(η-C₅H₄(CH₂)₂-μ-SPh)₂-Cl₂Rh(COD)]Cl.     

Übergangsmetall-Fulven-Komplexe: XXXI. Die Reaktivität des [η5-(C5H4CHO)M(CO)3]−-Anions (M  Mo,W) gegenüber Carbonsäurechloriden

The reactivity of the (η⁵-formylcyclopentadienyl)M(CO)₃ anions (M  Mo, W) towards acyl chlorides has been studied. Acetyl chloride reacts with the anions to give two different types of substituted cyclopentadienyl complexes: [M(Cl)(η⁵-C₅H₄CH₂OC(O)CH₃)(CO)₃] and [M(η¹-CH₃CO)(η⁵-CH₃CO)(η⁵-C₅H₄CH₂OC(O)CH₃)(CO)₃]. The reaction of the anions with benzoyl chloride only yields the chloro complexes [M(Cl)(η⁵-C₅H₄CH₂OC(O)C₆H₅)(CO)₃]. The molecular structure of [W(Cl)(η⁵-C₅H₄CH₂OC(O)CH₃)(CO)₃] has been determined by X-ray diffraction studies.     

Nickelocene chemistry : II. New methylidyne trinickel cluster compounds

The new methylidene trinickel cluster complexes, [RCNi₃(η⁵-C₅H₅₃] (R  CMe₃ or SiMe₃) and [Me₃SiCNi₃(η⁵-C₅H₅)2(η⁵-C₅H₄CH₂SiMe₃)] have been isolated in low yield from reactions between nickelocene and the corresponding alkyllithium reagents, RCH₂Li. The compounds [RCNi₃(η⁵-C₅H₅)₃] (R  Ph, CMe₃ or SiMe₃) have also been obtained by treatment of the σ-alkylnickel complexes [(η⁵-C₅H₅)Ni(CH₂R)(PPh₃)] with n-BuLi in the presence of an excess of nickelocene, but under similar conditions [(η⁵-C₅H₅)Ni(CH₂C_1OH₇-2)-(PPh₃)] (where C_1OH₇-2  2-naphthyl) failed to give [2-C_1OH₇CNi₃(η⁵-C₅H₅)₃]. The attempted synthesis of [(η⁵-C₅H₅)Ni(CH₂CCH)(PPh₃)] from [(η⁵-C₅H₅)-NiBr(PPh₃)] and CHCCH₂MgBr gave only [(η⁵-C₅H₅)Ni(CCMe)(PPh₃)] by an unusual rearrangement reaction.     

The mechanism of substitution of cymantrene derivatives by phosphines and phosphites

The kinetics of the thermal substitution of (η⁵-C₅H₄C(O)CH₃)Mn(CO)₂SC₄H₈, (η¹:η⁵-C₅H₄C(O)CH₂SCH₃)Mn(CO)₂ and (η¹:η⁵-C₅H₄C(O)CH₂CH₂SCH₃)Mn(CO)₂ by phosphines and phosphites have been measured in toluene and xylene. A proposed dissociative mechanism involving cleavage of the manganese–sulfur bonds as the rate-determining step is supported by the activation parameters obtained.     

Synthesis, characterization and the crystal structure of 1-[(N-methyl-N-aryl)amino]ethylferrocenes

The reactions of ferrocenylketimines [(η⁵-C₅H₄CCH₃NAr)Fe(η⁵-C₅H₅)] (Ar=a variety of substituted phenyls) with methyl-iodide in refluxed dichloromethane followed by reduction with sodium borohydride in absolute ethanol led to [(η⁵-C₅H₄CH(CH₃)N(CH₃)Ar)Fe(η⁵-C₅H₅)]. Compound [(η⁵-C₅H₄CH(CH₃)N(CH₃)C₆H₄Cl-p)Fe(η⁵-C₅H₅)] (3d) has been characterized structurally. Compound 3d is monoclinic, space group P2₁/n, with a=8.908(2) Å, b=13.63(1) Å, c=14.510(3) Å and β=107.03°.     

New alkenyl-substituted group 4 C-ansa-metallocene complexes. Reactivity of the substituent at the carbon ansa bridge

The allyl-substituted group 4 metal complexes [M{(R)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] [M = Ti, R = CH₂CHCH₂, (2); R = CH₂C(CH₃)CH₂ (3); M = Zr, R = CH₂CHCH₂ (4), R = CH₂C(CH₃)CH₂ (5)] have been synthesized by the reaction of allyl ansa-magnesocene derivatives and the tetrachloride salts of the corresponding transition metal. The dialkyl complexes ] [M = Ti, R = CH₂=CHCH₂, R′ = Me (6), R′ = CH₂Ph (7); R = CH₂C(CH₃)CH₂, R′ = Me (8), R′ = CH₂Ph (9); M = Zr, R = CH₂CHCH₂, R′ = Me (10), R′ = CH₂Ph (11); R = CH₂C(CH₃)CH₂, R′ = Me (12), R′ = CH₂Ph (13)] have been synthesized by the reaction of the corresponding ansa-metallocene dichloride complexes 2-5 and two molar equivalents of the alkyl Grignard reagent. Compounds 2-5 reacted with H₂ under catalytic conditions (Wilkinson’s catalyst or Pd/C) to give the hydrogenation products [M{(R)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] [M = Ti and R = CH₂CH₂CH₃ (14) or R = CH₂CH(CH₃)₂ (15); M = Zr and R = CH₂CH₂CH₃ (16) or R = CH₂CH(CH₃)₂ (17)]. The reactivity of 2-5 has also been tested in hydroboration and hydrosilylation reactions. The hydroboration reactions of 3, 4 and 5 with 9-borabicyclo[3.3.1]nonane (9-BBN) yielded the complexes [M{(9-BBN)CH₂CH(R)CH₂CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] [M = Ti and R = H (18); M = Zr and R = H (19) or R = CH₃ (20)]. The reaction with the silane reagents HSiMe₂Cl gave the corresponding [M{ClMe₂SiCH₂CHRCH₂CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] [M = Ti and R = H (21); M = Zr and R = H (22) or R = CH₃ (23)]. The reaction of 22 with t-BuMe₂SiOH produced a new complex [Zr{t-BuMe₂SiOSi(Me₂)CH₂CH₂CH₂CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}Cl₂] (24) through the formation of Si-O-Si bonds. On the other hand, reactivity studies of some zirconocene complexes were carried out, with the insertion reaction of phenyl isocyanate (PhNCO) into the zirconium-carbon σ-bond of [Zr{(n-Bu)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)}₂Me₂] (25) giving [{(n-Bu)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)]}Zr{Me{κ²-O,N-OC(Me)NPh}] as a mixture of two isomers 26a-b. The reaction of [Zr{(n-Bu)(H)C(η⁵-C₅Me₄)(η⁵-C₅H₄)}(CH₂Ph)₂] (27) with CO also provided a mixture of two isomers [{(n-Bu)CH(η⁵-C₅Me₄)(η⁵-C₅H₄)]}Zr(CH₂Ph){κ²-O,C-COCH₂Ph}] 28a-b. The molecular structures of 4, 11, 16 and 17 have been determined by single-crystal X-ray diffraction studies.