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Iron-ruthenium-osmium mixed trimetallic carbonyl clusters: Theoretical studies and structural trends

被引：13
作者：
Hunstock, E
Calhorda, MJ
Hirva, P
Pakkanen, TA
机构：
[1] Inst Tecnol Quim & Biol, EAN, P-2781901 Oeiras, Portugal
[2] Univ Lisbon, Fac Ciencias, Dept Quim Bioquim, P-1749016 Lisbon, Portugal
[3] Univ Joensuu, Dept Chem, FIN-80101 Joensuu, Finland
来源：
ORGANOMETALLICS | 2000年 / 19卷 / 22期
关键词：
D O I：
10.1021/om000512m
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The family of M-3(CO)(12) (M = Fe, Ru, Os) clusters, where Mg is any possible combination of Fe, Ru, and Os, was theoretically studied using DFT methods (ADF program). The optimized geometries were compared with the those of the clusters for which structures are available, and the agreement was quite good, especially when the metals were Fe and/or Ru. This allowed the prediction that the structure of the known, but not yet structurally characterized, Ru2Os(CO)(12) and RuOs2(CO)(12) clusters should be of the D-3 type, with only terminal carbonyls. On the other hand, the still unknown FeRuOs(CO)(12) cluster appears to prefer the C-2 form with two bridging carbonyls over the Fe-Ru edge, but the energy differs only by 2.7 kJ mol(-1) from that of the D-3 arrangement. The calculated enthalpy changes for the formation of mixed M-3(CO)(12) clusters, a process favored by entropy, are positive except for the formation of Ru2Os(CO)(12) and RuOs2(CO)(12) from the parent clusters, where the reaction is slightly exothermic.
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收藏
页码：4624 / 4628
页数：5
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