Attenuating Nucleophilicity of Titanocene Hydrides Beyond Steric Effects en Route to Fatty Alcohols.

Here, we introduce a new class of titanocene catalysts for epoxide hydrosilylation that frustrates their hydridicity and thereby emphasizes their electron transfer reactivity. This unique attenuation of hydridicity is accomplished by introducing Lewis acidic silicon centers to the cyclopentadienyl ligands for an intramolecular coordination of the titanium-bound hydride. The superiority of our rationally designed catalysts over classic titanocenes with alkyl-substituted cyclopentadienyl ligands is demonstrated in the dramatically improved regioselectivity of the hydrosilylation of monosubstituted epoxides to primary alcohols.

A Chiral Titanocene Complex as Regiodivergent Photoredox Catalyst: Synthetic Scope and Mechanism of Catalyst Generation.

We describe a combined synthetic, spectroscopic, and computational study of a chiral titanocene complex as a regiodivergent photoredox catalyst (PRC). With Kagan's complex catCl2 either monoprotected 1,3-diols or 1,4-diols can be obtained in high selectivity from a common epoxide substrate in a regiodivergent epoxide opening depending on which enantiomer of the catalyst is employed. Due to the catalyst-controlled regioselectivity of ring opening and the broader substrate scope, the PRC with catCl2 is also a highly attractive branching point for diversity-oriented synthesis. The photochemical processes of cat(NCS)2, a suitable model for catCl2, were probed by time-correlated single-photon counting. The photoexcited complex displays a thermally activated delayed fluorescence as a result of a singlet-triplet equilibration, S1 ⇄ T1, via intersystem crossing and recrossing. Its triplet state is quenched by electron transfer to the T1 state. Computational and cyclic voltammetry studies highlight the importance of our sulfonamide additive. By bonding to sulfonamide additives, chloride abstraction from [catCl2]- is facilitated, and catalyst deactivation by coordination of the sulfonamide group is circumvented.

Enantio- and Diastereomerically Pure Titanocenes by Dynamic Conformational Locking.

The synthesis of enantiomerically pure titanocenes is limited to cases with enantiomerically pure substituents at the cyclopentadienyl ligands and to ansa-titanocenes. For the latter complexes, the use of achiral ligands requires a resolution of enantiomers and frequently also a separation of the diastereoisomers obtained after metalation. Here, we introduce a new synthetic method that relies on the use of enantiomerically pure camphorsulfonate (CSA) ligands as control elements for the absolute and relative configuration of titanocene complexes. Starting from the conformationally flexible (RC5 H4 )2 TiCl2 , the desired conformationally locked and hence enantio- and diastereomerically pure complexes (RC5 H4 )2 Ti(CSA)2 are obtained in just two steps. According to X-ray crystallography the (RC5 H4 )2 Ti fragment is essentially C2 -symmetric and nuclear magnetic resonance displays overall C2 -symmetry. We applied density functional theory methods to unravel the dynamics of the complexes and the mechanisms and selectivities of their formation.