RONGALA RAMALAKSHMI, KOUSHIK SAHA, ANAMIKA PAUL Andsundargopal GHOSH*

SUPPLEMENTARY INFORMATION

Reactivity of [Cp*Mo(CO)3Me] with chalcogenated borohydrides Li[BH2E3] and Li[BH3EFc] (Cp* = (ɳ5-C5Me5); E = S, Se or Te; Fc = (C5H5-Fe-C5H4))

RONGALA RAMALAKSHMI, KOUSHIK SAHA, ANAMIKA PAUL andSUNDARGOPAL GHOSH*

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

Email:

*For Correspondence

List of Contents:

IExperimental Details

I.1Synthesis of chalcogeno-hydroborate ligands

I.2Spectroscopic Details

Figure S11H coupled 11B spectrum of Li[H3B(SFc)] from reaction between Fc2S2 and excess LiBH4 in THF.

Figure S21H coupled 11B spectrum of Li[H3B(SeFc)] from reaction between Fc2Se2 and excess LiBH4 in THF.

Figure S31H coupled 11B spectrum of Li[H3B(TeFc)] from reaction between Fc2Te2 and excess LiBH4 in THF.

Figure S41H NMR spectrum of compound 2.

Figure S513C NMR spectrum of compound 2.

Figure S6Infrared spectrum of compound 2.

Figure S7ESI+ Mass spectrum of compound 2.

Figure S81H NMR spectrum of compound 3.

Figure S913C NMR spectrum of compound 3.

Figure S10Infrared spectrum of compound 3.

Figure S11ESI+ Mass spectrum of compound 3.

Figure S121H NMR spectrum of compound 4.

Figure S1311B{1H} NMR spectrum of compound4.

Figure S1413C NMR spectrum of compound 4.

Figure S15Infrared spectrum of compound 4.

Figure S16ESI+ Mass spectrum of compound 4.

Figure S171H NMR spectrum of compound 5.

Figure S1811B{1H} NMR spectrum of compound5.

Figure S1913C NMR spectrum of compound 5.

Figure S2077Se spectrum of compound5.

Figure S21Infrared spectrum of compound 5.

Figure S22ESI+ Mass spectrum of compound 5.

Figure S231H NMR spectrum of compound 6.

Figure S2411B{1H} NMR spectrum of compound6.

Figure S2513C NMR spectrum of compound 6.

Figure S26125Te spectrum of compound6.

Figure S27Infrared spectrum of compound 6.

Figure S28ESI+ Mass spectrum of compound 6.

Figure S291H NMR spectrum of compound 7.

Figure S3013C NMR spectrum of compound 7.

Figure S31Infrared spectrum of compound 7.

Figure S32ESI+ Mass spectrum of compound 7.

Figure S331H NMR spectrum of compound 8.

Figure S3413C NMR spectrum of compound 8.

Figure S35Infrared spectrum of compound 8.

Figure S36ESI+ Mass spectrum of compound 8.

Figure S371H NMR spectrum of compound 9.

Figure S3813C NMR spectrum of compound 9.

Figure S39Infrared spectrum of compound 9.

Figure S40ESI+ Mass spectrum of compound 9.

IExperimental Details

I.1Synthesis of chalcogeno-hydroborate ligands:

Li[H3B(EFc)] ( E = S, Se, Te; Fc = C5H5-Fe-C5H4): The reaction of the 1.2 equiv. of [LiBH4.thf] (0.14 mL, 0.276 mmol) with [Fc2S2] (0.1 g, 0.230 mmol) in THF resulted Li[H3B(SFc)] and the 1H coupled 11B NMR of the reaction mixture displayed a quartet at δ = -28.2 ppm for Li[H3B(SFc)]. Similarly the Se and Te analogues prepared from [Fc2Se2] (0.1 g, 0.189 mmol) and [Fc2Te2] (0.1 g, 0.016 mmol) respectively. The quartret has been observed at δ = -27.1 and -34.4 ppm for Li[H3B(SeFc)] and Li[H3B(TeFc)] respectively.

Note that The 1H coupled 11B NMR of the reaction mixture has been compared with the reported values.1

Li[H3B(SFc)]: 11B NMR (128MHz): δ = -28.2 ppm.

Li[H3B(SeFc)]: 11B NMR (128MHz): δ = -27.1 ppm; 77Se NMR (95.38 MHz): δ = 207.2 ppm.

Li[H3B(TeFc)]: 11B NMR (128MHz): δ = -34.4 ppm; 125Te NMR (157.9 MHz): δ = 691.0 ppm.

Note that Li[BH2S3] has been prepared from reaction of [LiBH4.thf] with elemental sulfur in the ratio of 1:3 according to reported procedure.2In a similarly fashion, Se and Te analogues were prepared.3

I.2 Spectroscopic Details

Figure S1. 1H coupled 11B spectrum of Li[H3B(SFc)] from reaction between Fc2S2 and excess LiBH4 in THF.

Figure S2. 1H coupled 11B spectrum of Li[H3B(SeFc)] from reaction between Fc2Se2 and excess LiBH4 in THF.

Figure S3. 1H coupled 11B spectrum of Li[H3B(TeFc)] from reaction between Fc2Te2 and excess LiBH4 in THF.

Figure S4. 1H NMR spectrum of compound 2.

Figure S5. 13C NMR spectrum of compound 2.

Figure S6. Infrared spectrum of compound 2.

Figure S7. ESI+ Mass spectrum of compound 2.

Figure S8. 1H NMR spectrum of compound 3.

Figure S9. 13C NMR spectrum of compound 3.

Figure S10. Infrared spectrum of compound 3.

Figure S11. ESI+ Mass spectrum of compound 3.

Figure S12. 1H NMR spectrum of compound 4.

Figure S13. 11B{1H} NMR spectrum of compound4.

Figure S14. 13C NMR spectrum of compound 4.

Figure S15.Infrared spectrum of compound 4.

Figure S16. ESI+ Mass spectrum of compound 4.

Figure S17. 1H NMR spectrum of compound 5.

Figure S18. 11B{1H} NMR spectrum of compound5.

Figure S19. 13C NMR spectrum of compound 5.

Figure S20. 77Se spectrum of compound5.

Figure S21.Infrared spectrum of compound 5.

Figure S22. ESI+ Mass spectrum of compound 5.

Figure S23. 1H NMR spectrum of compound 6.

Figure S24. 11B{1H} NMR spectrum of compound6.

Figure S25. 13C NMR spectrum of compound 6.

Figure S26. 125Te spectrum of compound6.

Figure S27.Infrared spectrum of compound 6.

Figure S28. ESI+ Mass spectrum of compound 6.

Figure S29. 1H NMR spectrum of compound 7.

Figure S30. 13C NMR spectrum of compound 7.

Figure S31. Infrared spectrum of compound 7.

Figure S32. ESI+ Mass spectrum of compound 7.

Figure S33.1H NMR spectrum of compound 8.

Figure S34.13C NMR spectrum of compound 8.

Figure S35. Infrared spectrum of compound 8.

Figure S36. ESI+ Mass spectrum of compound 8.

Figure S37.1H NMR spectrum of compound 9.

Figure S38.13C NMR spectrum of compound 9.

Figure S39. Infrared spectrum of compound 9.

Figure S40. ESI+ Mass spectrum of compound 9.

References

1.(a) Ramalakshmi R, Saha K, Roy D K, Varghese B, Phukan A K and Ghosh S 2015 Chem. Eur. J.21 17191; (b) Mock M T,Potter R G, Camaioni D M,Li J,Dougherty W G,Kassel W S,Twamley B and DuBois D L 2009J. Am. Chem. Soc.13114454

2.Lalancette J M,Frêche A andMonteux R1968 Can. J. Chem.462754

3.Lalancette J M and Arnac M1969 Can. J. Chem.47 3695