Xiaohui Kang

Dinitrogen Cleavage and Hydrogenation by a Trinuclear Titanium Polyhydride Complex

Titanium Cleaver A century after its discovery, the Haber Bosch process is still used to produce ammonia from nitrogen for fertilizer. Nonetheless, the process requires high temperature and pressure, and chemists continue to look for synthetic analogs to microbial nitrogenase enzymes, which have managed to slice through the N2 triple bond under ambient conditions for millennia. Most efforts in this vein have relied on a boost from the reducing power of alkali metals. Shima et al. (p. 1549; see the Perspective by Fryzuk) instead explored the reactivity of a titanium hydride cluster, which cleanly slices through N2 at room temperature and incorporates the separated N atoms into its framework. Though ammonia was not produced, the system offers hope in the search for mild nitrogen reduction catalysts. The collective reactivity of three hydride-bridged titanium centers cleaves dinitrogen under mild conditions. [Also see Perspective by Fryzuk] Both the Haber-Bosch and biological ammonia syntheses are thought to rely on the cooperation of multiple metals in breaking the strong N≡N triple bond and forming an N–H bond. This has spurred investigations of the reactivity of molecular multimetallic hydrides with dinitrogen. We report here the reaction of a trinuclear titanium polyhydride complex with dinitrogen, which induces dinitrogen cleavage and partial hydrogenation at ambient temperature and pressure. By 1H and 15N nuclear magnetic resonance, x-ray crystallographic, and computational studies of some key reaction steps and products, we have determined that the dinitrogen (N2) reduction proceeds sequentially through scission of a N2 molecule bonded to three Ti atoms in a μ-η1:η2:η2-end-on-side-on fashion to give a μ2-N/μ3-N dinitrido species, followed by intramolecular hydrogen migration from Ti to the μ2-N nitrido unit.

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster

Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

Regio- and stereospecific living polymerization and copolymerization of (E)-1,3-pentadiene with 1,3-butadiene by half-sandwich scandium catalysts

The living isospecific-cis-1,4-polymerization and block-copolymerization of (E)-1,3-pentadiene with 1,3-butadiene have been achieved for the first time by using cationic half-sandwich scandium catalysts.