Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis

The alkylaluminum-complexed zirconocene trihydride cation [(SBI)Zr(μ-H)_3(AliBu_2)_2]^+, which is obtained by reaction of (SBI)ZrCl_2 with [Ph_3C][B(C_6F_5)_4] and excess HAl^iBu_2 in toluene solution, catalyzes the formation of isotactic polypropene when exposed to propene at -30 °C. This cation remains the sole observable species in catalyst systems free of AlMe compounds. In the presence of AlMe_3, however, exposure to propene causes the trihydride cation to be completely converted, under concurrent consumption of all hydride species by propene hydroalumination, to the doubly Me-bridged cation [(SBI)Zr(μ-Me)_2AlMe_2]^+. The latter then becomes the resting state for further propene polymerization, which produces, by chain transfer to Al, mainly AlMe_2-capped isotactic polypropene

Alkylaluminum-complexed zirconocene hydrides: identification of hydride-bridged species by NMR spectroscopy

Reactions of unbridged zirconocene dichlorides, (R_nC_5H_5−n)_2ZrCl_2 (n = 0, 1, or 2), with diisobutylaluminum hydride (HAl^iBu_2) result in the formation of tetranuclear trihydride clusters of the type (R_nC_5H_5−n)_2Zr(μ-H)_3(Al^iBu_2)_3(μ-Cl)_2, which contain three [Al^iBu_2] units. Ring-bridged ansa-zirconocene dichlorides, Me_2E(R_nC_5H_4−n)_2ZrCl_2 with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me_2E(R_nC_5H_4−n)_2Zr(Cl)(μ-H)_2Al^iBu_2 with only one [Al^iBu_2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C_5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAl^iBu_2 or Al^iBu_3, are proposed to be species of the type Me_2Si(ind)_2Zr(Me)(μ-H)_2Al^iBu_2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO

Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations

The ansa-zirconocene complex rac-Me_2Si(1-indenyl)_2ZrCl_2 ((SBI)ZrCl_2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)_3(Al^iBu_2)_2]^+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)_3(Al^iBu2)_2]^+ reacts reversibly with ClAl^iBu_2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)_2Al^iBu_2]^+. Reaction with AlMe_3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)_3(AlMe_x^iBu_(2−x))_2^]+ by exchange of alkyl groups between aluminum centers. At higher AlMe_3/Zr ratios, [(SBI)Zr(μ-Me)_2AlMe_2]^+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)_3(AlR_2)_2]^+ strongly predominates at comparable HAl^iBu_2 and AlMe_3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems

Catalyst Speciation During ansa-Zirconocene-Catalyzed Polymerization of 1-Hexene Studied by UV-vis Spectroscopy—Formation and Partial Re-Activation of Zr-Allyl Intermediates

Catalyst speciation during polymerization of 1-hexene in benzene or toluene solutions of the catalyst precursor SBIZr(μ-Me)_2AlMe_2^+ B(C_6F_5)_4^− (SBI = rac-dimethylsilyl-bis(1-indenyl)) at 23 °C is studied by following the accompanying UV-vis-spectral changes. These indicate that the onset of polymerization catalysis is associated with the concurrent formation of two distinct zirconocene species. One of these is proposed to consist of SBIZr-σ-polyhexenyl cations arising from SBIZr-Me^+ (formed from SBIZr(μ-Me)_2AlMe_2^+ by release of AlMe_3) by repeated olefin insertions, while the other one is proposed to consist of SBIZr-η^3-allyl cations of composition SBIZr-η^3-(1-R-C_3H_4)^+ (R = n-propyl), formed by σ-bond metathesis between SBIZr-Me^+ and 1-hexene under release of methane. At later reaction stages, all zirconocene-σ−polymeryl cations appear to decay to yet another SBIZr-allyl species, i.e., to cations of the type SBIZr- η^3-(x-R-(3-x)-pol-C_3H_3)^+ (pol = i-polyhexenyl, x = 1 or 2). Renewed addition of excess 1-hexene is proposed to convert these sterically encumbered Zr-allyl cations back to catalytically active SBIZr-σ−polymeryl cations within a few seconds, presumably by initial 1-hexene insertion into the η^1- isomer, followed by repeated additional insertions, while the initially formed, less crowded allyl cations, SBIZr-η^3-(1-R-C_3H_4)^+ appear to remain unchanged. Implications of these results with regard to the kinetics of zirconocene-catalyzed olefin polymerization are discussed

Versatile Coordination of Cyclopentadienyl-Arene Ligands and Its Role in Titanium-Catalyzed Ethylene Trimerization

Cationic titanium(IV) complexes with ansa-(η5-cyclopentadienyl,η6-arene) ligands were synthesized and characterized by X-ray crystallography. The strength of the metal-arene interaction in these systems was studied by variable-temperature NMR spectroscopy. Complexes with a C1 bridge between the cyclopentadienyl and arene moieties feature hemilabile coordination behavior of the ligand and consequently are active ethylene trimerization catalysts. Reaction of the titanium(IV) dimethyl cations with CO results in conversion to the analogous cationic titanium(II) dicarbonyl species. Metal-to-ligand backdonation in these formally low-valent complexes gives rise to a strongly bonded, partially reduced arene moiety. In contrast to the η6-arene coordination mode observed for titanium, the more electron-rich vanadium(V) cations [cyclopentadienyl-arene]V(NiPr2)(NC6H4-4-Me)+ feature η1-arene binding, as determined by a crystallographic study. The three different metal-arene coordination modes that we experimentally observed model intermediates in the cycle for titanium-catalyzed ethylene trimerization. The nature of the metal-arene interaction in these systems was studied by DFT calculations.

Bonding in complexes of bis(pentalene)di-titanium, Ti2(C8H6)2

Bonding in the bis(pentalene)di-titanium ‘double-sandwich’ species Ti2Pn2 (Pn = C8H6) and its interaction with other fragments have been investigated by xdensity functional calculations and fragment analysis. Ti2Pn2 with C2v symmetry has two metal-metal bonds and a low-lying metal based empty orbital, all three frontier orbitals having a1 symmetry. The latter may be regarded as being derived by symmetric combinations of the classic three frontier orbitals of two bent bis(cyclopentadienyl) metal fragments. Electrochemical studies on Ti2Pn†2 (Pn† = C8H4{SiiPr3-1,4}2) reveal a one-electron oxidation, and the formally mixed-valence Ti(II)-Ti(III) cationic complex [Ti2Pn†2][B(C6F5)4] has been structurally characterised. Theory indicates an S = ½ ground state electronic configuration for the latter, confirmed by EPR spectroscopy and SQUID magnetometry. Carbon dioxide binds symmetrically to Ti2Pn2 preserving C2v symmetry, as does carbon disulfide. The dominant interaction in Ti2Pn2CO2 is σ donation into the LUMO of bent CO2 and donation from the O atoms to Ti2Pn2 is minimal, whereas in Ti2Pn2CS2 there is significant interaction with the S atoms. The bridging O atom in the mono(oxo) species Ti2Pn2O, however, employs all three O 2p orbitals in binding and competes strongly with Pn, leading to weaker binding of the carbocyclic ligand, and the sulfur analog Ti2Pn2S behaves similarly. Ti2Pn2 is also capable of binding one, two and three molecules of carbon monoxide. The bonding demands of a single CO molecule are incompatible with symmetric binding and an asymmetric structure is found. The dicarbonyl adduct Ti2Pn2(CO)2 has Cs symmetry with the Ti2Pn2 unit acting as two MCp2 fragments. Synthetic studies show, that in the presence of excess CO a tricarbonyl complex Ti2Pn†2(CO)3 is formed, which optimises to an asymmetric structure with two terminal CO ligands and one semi-bridging. Low temperature 13C NMR spectroscopy reveals a rapid dynamic exchange between the two bound CO sites and free CO

Formation of Trivalent Zirconocene Complexes from ansa-Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study

Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. The chloro-bridged heterodinuclear ansa-zirconocenium cation [(SBI)Zr(μ-Cl)_2AlMe_2]^+ (SBI = rac-dimethylsilylbis(1-indenyl)), present in toluene solution as its B(C_6F_5)_4^– salt, thus gives rise to an EPR signal assignable to the complex (SBI)Zr^(III)(μ-Cl)_2AlMe_2, while (SBI)ZrIII-Me and (SBI)Zr^(III)(μ-H)_2Al^(i)Bu_2 are formed by reduction of [(SBI)Zr(μ-Me)_2AlMe_2]^+ B(C_6F_5)_4– and [(SBI)Zr(μ-H)_3(AliBu_2)_2]^+ B(C_6F_5)_4^–, respectively. These products can also be accessed, along with (SBI)ZrIII-iBu and [(SBI)ZrIII]^+ AlR_4^–, when (SBI)ZrMe_2 is allowed to react with HAl^(i)Bu_2, eliminating isobutane en route to the Zr(III) complex. Further studies concern interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation