| Sumario: | Reaction of laser-ablated Zr with CH (CH, CD, and CHD) in excess neon during condensation at 5 K forms CH == ZrH, the simplest alkylidene hydride complex, which is identified by infrared absorptions at 1581.0, 1546.2, 757.0, and 634.5 cm. Density functional theory electronic structure calculations using a large basis set with polarization functions predict a C symmetry structure with agostic C--H- - -Zr bonding and distance of 2.300 Å. Identification of the agostic CH == ZrH methylidene complex is confirmed by an excellent match of calculated and observed isotopic frequencies particularly for the four unique CHD==ZrHD isotopic modifications. The analogous reactions in excess argon give two persistent photoreversibie matrix configurations for CH==ZrH. Finally, methane activation by, CH==ZrH gives the new (CH)ZrH molecule.
|
|---|