混合价簇合物[Et_4N]_2[{(CO)_4M}_xM′S_4][x=1,2;M=Mo(0)或W(0);M′=Mo(Ⅵ)或W(Ⅵ)]的共振Raman光谱及IR光谱研究  

Studies on the Resonance-Raman and Infrared Spectra of Cluster Compounds with Mixed-Valence Mo(W) Atoms, [Et_4N]_2[{(CO)_4M}_xM'S_4] [x= 1 or 2, M= Mo(0) or W(0), M'= Mo(Ⅵ) or W(Ⅵ)]

作　　者：何玲洁[1] 余佩华[1] 庄伯涛[1] 蔡素华[1] 陈波[1] 张琳娜[1] 朱自莹 傅桂香[2] 谭暎 

机构地区：[1]中国科学院福建物质结构研究所,福州350002 [2]中国科学院上海有机化学研究所,上海200032

出　　处：《化学学报》1995年第11期1093-1100,共8页Acta Chimica Sinica

基　　金：国家自然科学基金;结构化学国家重点实验室资助的项目

摘　　要：研究了[{(CO)4_M}_xM′S_4]^(2-)[X=1,2;M=Mo(O),W(O);M′=Mo(Ⅵ),W(Ⅵ)]系列簇合物的共振Raman(RR)光谱及红外(IR)光谱.除了对:v_(c—o),v_(M(Ⅵ)—S(b))[S(b):桥基S],v_(M(Ⅵ)—S(t))[S(t):端基S],v_(M(o)—c),δ_(M(O)—C—O)进行归属外,着重讨论v_(M(O)—S(b)),v_(M(O)-M(Ⅵ))的归属.研究了IR谱中Δv[v_(M(Ⅵ)—S(b))(—v)_(M(O)—S(b))]与M(0)→M(Ⅵ)电荷迁移的关系.RR谱研究结果表明,在[(CO)_(4-)MS_2MoS_2]^(2-),[(CO)_4MoS_2MoS_2Mo(CO)_4]^(2-)中S(b)一M(0)电荷迁移与M(0)-MO(Ⅵ)电荷迁移之间有较明显的相互偶合;在[(CO)_4MS_2WS_2]^(2-)中S(b)→W(Ⅵ)与M(O)→W(Ⅵ)电荷迁移、S(t)→W(Ⅵ)与M(0)→W(Ⅵ)电荷迁移之间也分别存在明显的相互偶合,说明了它们存在强的电子离域.本系列簇合物中二核簇的电子离域程度比三核簇强.The Resonance-Ramsn and Infrared spectra of series of cluster compounds, [{(CO)4M}x-M'S4]2- [x= 1 or 2; M =Mo(0) or W(0); M'=Mo(Ⅵ) or W(Ⅵ)] have been investigated. Besides the characteristic frequencies of vco, vM(VI)_s(b),vM(Ⅵ)-s(t), v(0)-C and 5M(0)-C-O were assigned. The assignment of vM(0)-s(b) and VM(0)-M(Ⅵ) were emphatically discussed. The relationship between Δv [vM(Ⅵ)-s(b)-vM(0)-s(b)] and M(0)→M(Ⅵ) charge transfer were demonstrated by their IR spectra. The results from the studies on the Resonance-Raman spectra indicate that there evidently are couplings between the S(b)→Mo(0) charge transfer and M(0)→Mo(Ⅵ) charge transfer in [(CO)4MS2MoS2]2- and [(CO)4MoS2MoS2Mo(CO)4]2- between S(b)→W(Ⅵ) and M(0)→W(Ⅵ) charge transfer and between S(t)→W(Ⅵ) and M(0)→W(Ⅵ) charge transfer in [(CO)4MS2WS2]2-. This implies that the extensive electron delocalization exists in these cluster compounds with mixed-valence metal atoms and the electron delocalization in the dinuclear clusters is stronger than that in the trinuclear clusters.

关 键 词：混合价 原子簇 红外光谱 散射谱 钙 钨 

分 类 号：O641.4[理学—物理化学] O657.3[理学—化学]