Journal
INORGANICS
Volume 9, Issue 4, Pages -Publisher
MDPI
DOI: 10.3390/inorganics9040028
Keywords
cobaltaborane; decaborane; eleven-vertex cluster; nido cluster; metallaborane; mixed-metal cluster; ten-vertex cluster
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Funding
- Department of Science and Technology, India, DST-INSPIRE
- IIT Madras
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The synthesis, isolation, and structural characterization of unique metal-rich, diamagnetic cobaltaborane clusters were reported in this study. These clusters were obtained from reactions of different reagents with cobalt sources. Characterization of the compounds was carried out using various techniques, and density functional theory calculations were used to study the bonding and electronic structures of these complexes in depth.
Synthesis, isolation, and structural characterization of unique metal rich diamagnetic cobaltaborane clusters are reported. They were obtained from reactions of monoborane as well as modified borohydride reagents with cobalt sources. For example, the reaction of [Cp*CoCl](2) with [LiBH4 center dot THF] and subsequent photolysis with excess [BH3 center dot THF] (THF = tetrahydrofuran) at room temperature afforded the 11-vertex tricobaltaborane nido-[(Cp*Co)(3)B8H10] (1, Cp* = eta(5)-C5Me5). The reaction of Li[BH2S3] with the dicobaltaoctaborane(12) [(Cp*Co)(2)B6H10] yielded the 10-vertex nido-2,4-[(Cp*Co)(2)B8H12] cluster (2), extending the library of dicobaltadecaborane(14) analogues. Although cluster 1 adopts a classical 11-vertex-nido-geometry with one cobalt center and four boron atoms forming the open pentagonal face, it disobeys the Polyhedral Skeletal Electron Pair Theory (PSEPT). Compound 2 adopts a perfectly symmetrical 10-vertex-nido framework with a plane of symmetry bisecting the basal boron plane resulting in two {CoB3} units bridged at the base by two boron atoms and possesses the expected electron count. Both compounds were characterized in solution by multinuclear NMR and IR spectroscopies and by mass spectrometry. Single-crystal X-ray diffraction analyses confirmed the structures of the compounds. Additionally, density functional theory (DFT) calculations were performed in order to study and interpret the nature of bonding and electronic structures of these complexes.
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