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Design, Structural Characterization and Catalytic Activity of Incomplete Dicubane Clusters of N-Substituted Diethanolamines

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Abstract

A series of four new clusters with cationic unit [Co4(µ3-OH)(Rdea)2(L–L)4]4+ [R = –CH3 (1 and 2) or –CH2CH2CH2CH3 (3 and 4), L–L = 1,10-phenanthroline or 2,2′-bipyridine] is designed and characterized by elemental, spectroscopic (FTIR, ESI MS, UV–visible), thermal, electrochemical, magnetic, SEM, EDX, PXRD and single crystal X-ray crystallographic techniques. Spectral and single crystal X-ray studies reveal the complexes 1–4 are tetranuclear clusters where the primary aminoalcohol derivative ligand is present in dianionic form i.e., Medea2− or nBudea2−. It is confirmed from the magnetic and bond valence summation data that the four cobalt ions are present in mixed valent states (Co 2+2 –Co 3+2 ), which is further corroborated from the Co–O and Co–N bond lengths in X-ray structure. The bridging two hydroxide ions consolidate the tetranuclear clusters by bonding with three neighboring metal ions and a rare incomplete dicubane core is formed in all the complexes. A supramolecular framework is generated by H-bonding, π–π, CH···π, and H···H interactions. Presence of N-alkyl group and N-heterocyclic chelator facilitates the generation of these non covalent interactions thus stabilizing the framework. Of all the complexes reported here, 1 is found most efficient catalyst for the cobalt-catalyzed aerobic oxidation of neat ethylbenzene and p-xylene.

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Acknowledgements

The authors are thankful to the Chairman, Department of Chemistry, Aligarh Muslim University, Aligarh, India, for providing necessary facilities. Farasha Sama thanks UGC, New Delhi for Senior Research Fellowship. M. Shahid acknowledges SERB-DST, New Delhi for financial assistance (Ref. No. SR/FT/CS-76/2011) and Z. A. Siddiqi thanks UGC, New Delhi for UGC BSR faculty fellowship.

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  1. Department of Chemistry, Aligarh Muslim University, Aligarh, 202002, India

    Farasha Sama, Istikhar A. Ansari, Mukul Raizada, Mo. Ashafaq, M. Shahid & Zafar A. Siddiqi

  2. Department of Applied Chemistry, Aligarh Muslim University, Aligarh, 202002, India

    Musheer Ahmad

  3. Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati, India

    Babulal Das & Krapa Shankar

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  1. Farasha Sama
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Sama, F., Ansari, I.A., Raizada, M. et al. Design, Structural Characterization and Catalytic Activity of Incomplete Dicubane Clusters of N-Substituted Diethanolamines. J Clust Sci 28, 1355–1377 (2017). https://doi.org/10.1007/s10876-016-1145-1

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