H-bridged A(3)H(3)(+) (A=Si and Ge): A pi-ligand in organometallic chemistry

摘要

Organometallic complexes based on H-bridged Si3H3+ and Ge3H3+ ligands were studied at the B3LYP and B3P86 levels. Relativistic effective core potentials (SBKJC-21G and Stuttgart-RSC) and their associated basis sets were used on metals and the 6-31G(d) basis set was used on ligands. All the complexes (A(3)H(3))Co(CO)(3) (9, C-3v), (A(3)H(3))Rh(CO)(3) (10, C-3v) and (A(3)H(3))Ir(CO)(3) (11, C-3v) (A = Si and Ge) are minima and more stable than the complexes based on Si3H3+ and Ge3H3+ ligands with terminal hydrogens (9a-11a). The stability of the bridged systems increases from Si to Ge. Isolobal and isosynaptic analogies connect these complexes with other organometallic complexes (e.g. (mu-H)(3)Fe-3 (CO)(9) (mu(3)-CMe)) and main group pyramidal systems (e. g. (mu-H)(3)B3H3 (mu(3)-CH)). [References: 61]