The π-η5:σ-η1 coordination mode of early transition metal pentafulvene ligands yields a strongly nucleophilic exocyclic carbon atom (Cexo). The substitution of the chlorido ligand of bis(η5:η1-(di-p-tolyl)pentafulvene)niobium chloride (1) by reaction...

Titanium FLPs! Solvent- and catalyst-free Aza-Michael reaction provides β-amino ketones which were employed as ligand precursors for the convenient synthesis of novel cationic titanium complexes with tridentate Cp,O,N-ligand frameworks, which activate C–X bonds in a FLP-like manner.

The synthesis and characterization of triazenido complexes of the group IV metals zirconium and hafnium is reported. The reaction of the group IV pentafulvene complexes Cp*(π–η5:σ–η1-pentafulvene)-zirconium(IV) and -hafnium(IV)chlorides with the sterically demanding 2,6-dimesitylphenyl azide results in the insertion of the γ-nitrogen atom of the ligand precursor into the polarized M–Cexo (Cexo: exocyclic carbon atom) bond of the pentafulvene ligand, forming a formal Cp,N,N tridentate ligand system. The molecular structures of the furnished complexes reveal the rare κ1 N coordination of the γ-nitrogen atom to the zirconium or hafnium center along with a localized Nα–Nβ double bond. Unusually, in one case, the ligand system shows additional coordination of the α-nitrogen atom to the central metal atom and well-balanced N–N distances, thus, forming the chelating κ2 N,N coordination mode of the triazenido ligand. The potential use of the formed complexes as precursors for cationic group IV cationic complexes was investigated by reaction with methyl lithium.

The benzene ligand at CpV(η 6 À C 6 H 6 ) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 a and 2 b) and benzofulvene complexes (3 a and 3 b). The molecular structures of the target compounds suggest a π-η 5 :σ-η 1 coordination mode with a vanadium III center. With the sterically low demanding 6,6-dimethylpentafulvene, a CÀ H activation at the leaving ligand is observed, yielding the ring-substituted vanadocene II 4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadocene III compounds were synthesized: Under mild conditions, EÀ H splitting of 4tert-butylphenol, diphenylamine, and 2,6-diisopropylaniline yield well characterized examples of rare vanadocene III phenolate and amide complexes. Insertion reactions into the VÀ C exo bond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4-chlorobenzonitril and N,N'-dicyclohexylcarbodiimide.

Addition of the parent allene H2CCCH2 to the bis(pentafulvene)titanium complexes Ti1a,b results in the formal nucleophilic attack of one of the exocyclic quaternary carbon atoms (Cq,exo) of one pentafulvene ligand at the central propa-1,2-diene carbon atom to form the titanium complexes Ti2a,b bearing both one intact pentafulvene ligand and a bidentate cyclopentadienyl-/allyl-based ligand, whose functionalities are spaced by a C1 linker. Investigations into the nature of the Ti–allyl interaction is established by multinuclear NMR spectroscopy, single crystal X-ray diffraction, and combined computational studies. A first glimpse of the reactivity of Ti2a,b is demonstrated showing that both the intact pentafulvene ligand and the allyl unit can be modified.