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HomeAdvanced Materials ResearchAdvanced Materials Research Vol. 924Characterizations of Novel Binuclear Transition...

Characterizations of Novel Binuclear Transition Metal Polynitrogen Compounds: M₂(N₅)₄ (M=Co, Rh and Ir)

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Abstract:

Theoretical studies on a series of binuclear transition metal pentazolides M₂(N₅)₄ (M=Co, Rh and Ir) predict Paddlewheel-type structures with very short metal-metal distances suggesting high-order metal-metal multiple bonds. Natural Bonding Orbital (NBO) analysis have indicated that the bonding between the metal atom and the five-membered ring is predominantly ionic for each M₂(N₅)₄ species, and a high-order metal-metal multiple bonding exists between the two metal atoms, in addition, the presence of the delocalized π orbital plays an important role in the stabilization of this metal-polynitrogen species. Nucleus independent chemical shift (NICS) values confirm that the planar N₅ exhibits aromaticity in these M₂(N₅)₄ species. The values of NICS(0.0), NICS(0.5) and NICS(1.0) for Co₂(N₅)₄ are larger than those of the other two M₂(N₅)₄ species (M=Rh and Ir), with the order of Co₂(N₅)₄>Rh₂(N₅)₄>Ir₂(N₅)₄. The dissociation energies into Mononuclear Fragments for M₂(N₅)₄ (M=Co, Rh and Ir) are predicted to be 82.9 (85.7), 139.9 (113.2), and 155.1 (149.7) kcal/mol, respectively. However, the dissociation energies for the loss of one pentazolato group from the M₂(N₅)₄ analysis have indicated that the Co₂(N₅)₄ is relatively higher at ~40 kcal/mol. Thermochemistry suggests Co₂(N₅)₄ to be a viable species.

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Advanced Materials Research (Volume 924)

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233-252

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https://doi.org/10.4028/www.scientific.net/AMR.924.233

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April 2014

Authors:

Li Hong Tang, Hui Bin Guo, Qian Shu Li*, Jin Hui Peng, Jun Jie Gu, Li Bai Xiao

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Density Functional Calculations, N Ligands, Natural Bonding Orbital, Polynitrogen

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