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Reactivity of [Cp*Mo(CO)3Me] with chalcogenated borohydrides Li[BH2E3] and Li[BH3EFc] (Cp*= (η 5-C5Me5); E = S, Se or Te; Fc = (C5H5-Fe-C5H4))

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Abstract

Reactivity of [Cp*Mo(CO) 3Me], 1 with various chalcogenide ligands such as Li[BH 2 E 3] and Li[BH 3EFc] (E = S, Se or Te; Fc = (C 5 H 5-Fe-C 5 H 4)) has been described. Room temperature reaction of 1 with Li[BH 2 E 3] (E = S and Se) yielded metal chalcogenide complexes [Cp*Mo(CO) 2(η 2-S 2 CCH 3)], 2 and [Cp*Mo(CO) 2(η 1-SeC 2 H 5)], 3. In compound 2, {Cp*Mo(CO) 2} fragment adopts a four-legged piano-stool geometry with a η 2-dithioacetate moiety. In contrast, treatment of 1 with Li[BH 3(EFc)] (E = S, Se or Te; Fc = C 5 H 5-Fe-C 5 H 4) yielded borate complexes [Cp*Mo(CO) 2(μ-H)(μ-EFc)BH 2], 4-6 in moderate yields. Compounds 4-6 are too unstable and gradual conversion to [{Cp*Mo(CO) 2} 2(μ-H)(μ-EFc] (7: E = S; 8: Se) and [{Cp*Mo(CO) 2} 2(μ-TeFc) 2], 9 happened by subsequent release of BH 3. All the compounds have been characterized by mass spectrometry, IR, multinuclear NMR spectroscopy and structures were unequivocally established by crystallographic analysis for compounds 2, 3 and 7.

Reactivity of [Cp*Mo(CO)3Me] with various chalcogenide ligands such as, Li[BH2E3] and Li[BH3EFc] (E = S, Se or Te; Fc = (C5H5-Fe-C5H4)), generated novel molybdenum thiolate and agostic borate complexes respectively.

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Acknowledgements

Generous support of the Department of Science and Technology, DST (Project No. SR/SI/IC-13/2011), New Delhi is gratefully acknowledged. R. R. is grateful to University Grants Commission (UGC) and K. S. is thankful to Council of Scientific and Industrial Research (CSIR), India for Research Fellowship.

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  1. Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, India

    RONGALA RAMALAKSHMI, KOUSHIK SAHA, ANAMIKA PAUL & SUNDARGOPAL GHOSH

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Correspondence to SUNDARGOPAL GHOSH.

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Supplementary Information (SI)

Supplementary data contains the X-ray crystallographic files in CIF format for 2, 3, 7 and CCDC 1431592 (2), 1431593 (3), 1431591 (7) for this work. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_-request/cif. All additional information pertaining to characterization of the complexes 2-9 using ESI-MS technique, IR spectra and multinuclear NMR spectra and 1H coupled 11B spectra of Li[H 3B(EFc)] (E = S, Se, Te), (figures S1–S40) are given in the Supplementary Information, available at www.ias.ac.in/chemsci.

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RAMALAKSHMI, R., SAHA, K., PAUL, A. et al. Reactivity of [Cp*Mo(CO)3Me] with chalcogenated borohydrides Li[BH2E3] and Li[BH3EFc] (Cp*= (η 5-C5Me5); E = S, Se or Te; Fc = (C5H5-Fe-C5H4)). J Chem Sci 128, 1025–1032 (2016). https://doi.org/10.1007/s12039-016-1102-4

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