Electronic Structure and Chemical Bonding of La7Os4C9

In the recently synthesized rare earth transition metal carbide $La_7O_{s4}C_9$ one finds one-dimensional organometallic $[O_{s4}C_9]^{21-}$ polymers embedded in a $La^{3+}$ ionic matrix. The electronic structure of the polymeric $[O_{s4}C_9]^{21-}$ chain was investigated by density of states (DOS) and crystal orbital overlap population (COOP), using the extended Huckel algorithm. A fragment molecular orbital analysis is used to study the bonding characteristics of the $C_2$ units in $La_7O_{s4}C_9$ containing $C_2$ units and single C atoms as well. The title compound contains partially filled Os and carbon bands leading to metallic conductivity. As the observed distances already indicated, the calculations show extensive Os-C interactions. The C-C bond distance in the diatomic $C_2$ units ($d_{C-C}$=131 pm) in the solid is significantly increased relative to $${C_2}^{2-}$$ or acetylene, because antibonding $1{\pi}_g$ orbitals are partially filled by the Os-$C_2(1\;{\pi}_g)$ bonding contribution found at and below the Fermi level.

La7Os4C9의 전자구조와 화학결합

고체 화합물 La7Os4C9 속에 있는 [Os4C9]21‑ 사슬의 전자구조와 화학결합을 extended Hückel 계산 결과에 의해서 논의하였다. 탄소 원자는 물론 (C2)2‑ 분자의 결합 특성은 비교적 큰 Os-C 상호작용을 나 타내었고 특히 (C2)2‑ 분자의 결합길이 증가는 Fermi level 바로 아래에 Os-C2(1 πg) 결합 밴드의 존재로 인 해서 반결합 1πg 오비탈에 부분적인 전자점유가 일어나기 때문인 것으로 해석된다.