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RESEARCH ARTICLE
Contents Vol 67(9)

Major Differences Between Mononuclear and Binuclear Manganese Carbonyl Cyanides and Isoelectronic Binary Chromium Carbonyls Arising from Basicity of the Cyanide Nitrogen Atom*

Ruixue Jia A , Chaoyang Wang A , Luo Qiong A C , Qian-Shu Li A , Yaoming Xie B , R. Bruce King A B C and Henry F. Schaefer III B
+ Author Affiliations
- Author Affiliations

A Ministry of Education Key Laboratory of Theoretical Environmental Chemistry, Center for Computational Quantum Chemistry, South China Normal University, Guangzhou 510631, China.

B Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, GA 30602, USA.

C Corresponding authors. Email: kelly.luo@126.com; rbking@chem.uga.edu

Australian Journal of Chemistry 67(9) 1318-1323 https://doi.org/10.1071/CH14227
Submitted: 14 April 2014  Accepted: 7 May 2014   Published: 4 June 2014

Abstract

The manganese carbonyl cyanides Mn(CO)n(CN) and Mn2(CO)n(CN)2 have been investigated by density functional theory. The lowest energy structure for Mn(CO)5(CN) is found to be the experimentally known C-bonded cyanide. The experimentally unknown N-bonded Mn(CO)5(NC) lies ~60 kJ mol–1 above its cyanide isomer. The Mn(CO)4(CN) isomers are obtained by removal of a CO group in various ways from Mn(CO)5(CN) or Mn(CO)5(NC). Three structures, cyanide Mn(CO)3(CN), isocyanide Mn(CO)3(NC), and Mn(CO)3(η2-CN), are found for the tricarbonyl. All low-energy binuclear Mn2(CO)n(CN)2 structures have two end-to-end bridging CN groups. These two η2-CN bridges can be oriented in the same or opposite directions. The Mn2(CO)7(CN)2 structures of this type can be derived from these Mn2(CO)8(CN)2 structures by removal of a CO group with relatively little change in the remainder of the structure. These low-energy Mn2(CO)n(CN)2 structures (n = 8, 7) are very different from the previously studied isoelectronic Cr2(CO)n+2 structures in which low-energy end-to-end CO bridged structures are not found.


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