SUPPLEMENTARY INFORMATION

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1 SUPPLEMENTARY INFORMATION Cleave and Capture Chemistry: Synergic Fragmentation of THF Robert E. Mulvey 1*, Victoria L. Blair 1, William Clegg 2, Alan R. Kennedy 1, Jan Klett 1, Luca Russo 2 1 WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, U.K. 2 School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, U.K. * r.e.mulvey@strath.ac.uk Synthesis and Characterisation of Compounds 3, 4, 5 and 6. General Methods. n-hexane and THF were distilled from sodium-benzophenone, TMEDA was distilled from CaH 2. All synthetic work was carried out under an inert argon atmosphere using standard Schlenk and glove box techniques. 1 H and 13 C NMR spectra were recorded on either a Bruker AV 400 or Bruker DPX 400 and were referenced to the resonances of the [1] deuterated solvents used. Bis(trimethylsilylmethyl)magnesium Mg(CH 2 SiMe 3 ) 2 and bis(trimethylsilylmethyl)manganese Mn(CH 2 SiMe 3 ) [2,3] 2 were prepared according to literature procedures. The crude bis(trimethylsilylmethyl)magnesium was also purified via sublimation at 175 C (~10-2 torr) to furnish pure Mg(CH 2 SiMe 3 ) 2. Experimental Crystallography. Measurements were made either with an Enraf Nonius Kappa Diffractometer (4) or an Oxford Diffraction Xcalibur Sapphire system (5 and 6). All structures were refined to convergence against F 2 using programs from the SHELX family. [4] Selected parameters are summarized in the text and full details given in the supplementary cif files. 4 and 5 are well ordered and routinely modeled compounds. Although otherwise isostructural with 5, the structure of compound 6 appears somewhat disordered in the region of the captured dianion. After several trial calculations, the best model described a species with an 80% occupied butadiene site and a 20% occupied benzene site (both twice deprotonated). Whether the benzene fragment derives from an impurity in the starting materials or is formed in situ, possibly via further reaction of the butadiene fragments, is unknown. CCDC (4), CCDC (5) and CCDC (6) contain the supplementary crystallographic data for this publication. These data can be obtained free of nature chemistry 1

2 supplementary information charge at (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: ; deposit@ccdc.cam.ac.uk). Synthesis of [Na 2 Mg 2 (TMP) 4 (O)], 3 and [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5: TMPH (0.34 ml, 2.0 mmol) was added to a suspension of BuNa (0.08 g, 1.0 mmol) in dry n-hexane (20 ml) and the resultant mixture was allowed to stir at room temperature for 1 h. Mg(CH 2 SiMe 3 ) 2 (0.20 g, 1.0 mmol) and TMEDA (0.15 ml, 1.0 mmol) was added to give a light yellow solution. Next, THF (0.08 ml, 1.0 mmol) was added and the colourless solution was gently heated for 5 minutes. Upon cooling to room temperature large colourless needle crystals of 5 were deposited (0.23 g, 48.9 %). The mother liquor was subsequently further concentrated under vacuum and upon standing at room temperature colourless plate crystals of 3 were deposited (0.14 g, 41.7 %). mp (for 3): 202 ºC (decomposition); mp (for 5): 186 ºC (decomposition). NMR data for 3: 1 H NMR ( MHz, d 6 -benzene, 300 K): δ 1.98 (m, 1H, γ-ch 2, TMP), 1.74 (d (br), 3H, γ-ch 2, TMP & β-ch 2, TMP), 1.47 (s, 6H, CH 3 TMP), 1.26 (s, 6H, CH 3 TMP), 1.00 ppm (m (br), 2H, β-ch 2, TMP). 13 C NMR ( MHz, d 6 -benzene, 300 K): δ (α-c-tmp), 43.3 (β-ch 2, TMP), 39.1 (CH 3 -TMP), 34.3 (CH 3 -TMP), 19.9 ppm (γ-ch 2, TMP). NMR data for 5: 1 H NMR ( MHz, d 6 -benzene, 300 K): δ 6.75 (s, 4H, C 4 H 4 ), 2.18 (s, 8H, CH 2, TMEDA), 2.06 (s, 24H, CH 3, TMEDA), 1.68 (s (br), 48H, CH 3 TMP), 1.49 ppm ( s (br), 24H, γ-ch 2, TMP & β-ch 2, TMP). 1 H NMR ( MHz, d 8 -THF, 300 K): δ 6.50 (m, 2H, C 4 H 4 ), 6.36 (m, 2H, C 4 H 4 ), 2.30 (s, 8H, CH 2, TMEDA), 2.15 (s, 24H, CH 3, TMEDA), 1.67 (m, 8H, γ-ch 2, TMP), 1.24 (s (br), 48H, CH 3 TMP), 1.16 ppm ( m (br), 16H, β-ch 2, TMP). 13 C NMR ( MHz, d 8 -THF, 300K): (C B, C 4 H 4 ), (C A, C 4 H 4 ), (CH 2 -TMEDA), (α-c-tmp), (CH 3 -TMEDA), (β-ch 2, TMP), (CH 3 -TMP), ppm (γ-ch 2, TMP). Crystal data for 5: C 52 H 108 Mg 2 N 8 Na 2, M r = g/mol, monoclinic, space group P2 1 /n, a = (3), b = (8), c = (6) Å, β = (4), V = (19) Å 3, Z = 2, λ = Å, μ = mm -1, T = 123 K; reflections, 7797 unique, R int ; final refinement to convergence on F 2 gave R = (F, 5648 obs. data only) and R w = (F 2, all data), GOF = nature chemistry

3 supplementary information Figure S1. Molecular structure of 5 (on the 30% probability level). Selected hydrogen atoms have been omitted for clarity. Synthesis [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 D 4 }], 5(d 4 ): TMPH (0.34 ml, 2.0 mmol) was added to a suspension of BuNa (0.08 g, 1.0 mmol) in dry n-hexane (20 ml) and the resultant mixture was allowed to stir at room temperature for 1 h. Mg(CH 2 SiMe 3 ) 2 (0.20 g, 1.0 mmol) and TMEDA (0.15 ml, 1.0 mmol) was added to give a light yellow solution. Next, d 8 -THF (0.08 ml, 1.0 mmol) was added and the colourless solution was gently heated for 5 minutes. Upon cooling to room temperature large colourless needle crystals of 5(d 4 ) were deposited (0.18 g, 38.2 %). NMR data for 5(d 4 ): 1 H NMR ( MHz, d 6 -benzene, 300 K): δ 2.18 (s, 8H, CH 2, TMEDA), 2.06 (s, 24H, CH 3, TMEDA), 1.68 (s (br), 48H, CH 3 TMP), 1.49 ppm (s (br), 24H, γ-ch 2, TMP & β-ch 2, TMP). Synthesis of [Na 2 Mn 2 (TMP) 4 (O)], 4 and [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mn(TMP)] 2 - C 4 H 4 }], 6: TMPH (0.34 ml, 2.0 mmol) was added to a suspension of BuNa (0.08 g, 1.0 mmol) in dry n-hexane (20 ml) and the resultant mixture was allowed to stir at room temperature for 1 h. Mn(CH 2 SiMe 3 ) 2 (0.23 g, 1.0 mmol) and TMEDA (0.15 ml, 1.0 mmol) was added to give a light orange solution. Next, THF (0.08 ml, 1.0 mmol) was added and the solution allowed to stir at room temperature for 12 hrs. The red solution was filtered and concentrated slightly under vacuum. Allowing the solution to stand at room temperature for 1 week afforded red/orange needle crystals of 6 to form (0.25 g, 49.9 %). The mother liquor was further concentrated in vacuum to furnish light pink plate crystals of 4 (0.16 g, 43.6 %). mp (for 4): 192 ºC (decomposition); mp (for 6): 183 ºC (decomposition). nature chemistry 3

4 supplementary information Crystal data for 4: C 36 H 72 Mn 2 N 4 Na 2 O, M r = g/mol, monoclinic, space group P2 1 /n, a = (2), b = (2), c = (2) Å, β = (3), V = (7) Å 3, Z = 2, λ = Å, μ = mm -1, T = 150 K; reflections, 3539 unique, R int ; final refinement to convergence on F 2 gave R = (F, 2809 obs. data only) and R w = (F 2, all data), GOF = Figure S2. Molecular structure of 4 (on the 30% probability level). Hydrogen atoms have been omitted for clarity. 4 nature chemistry

5 supplementary information Crystal data for 6: C 52.4 H 108 Mn 2 N 8 Na 2, M r = g/mol, monoclinic, space group P2 1 /n, a = (3), b = (9), c = (7) Å, β = (4), V = (2) Å 3, Z = 2, λ = Å, μ = mm -1, T = 123 K; reflections, 7821 unique, R int ; final refinement to convergence on F 2 gave R = (F, 5597 obs. data only) and R w = (F 2, all data), GOF = Figure S3. Molecular structure of 6 (on the 30% probability level). Hydrogen atoms and minor disorder have been omitted for clarity. nature chemistry 5

6 supplementary information ppm Figure S4. 1 H NMR spectrum of [Na 2 Mg 2 (TMP) 4 (O)], 3 in d 6 -benzene ppm Figure S5. 13 C NMR spectrum of [Na 2 Mg 2 (TMP) 4 (O)], 3 in d 6 -benzene. 6 nature chemistry

7 supplementary information Figure S6. 1 H EXSY NMR spectrum of [Na 2 Mg 2 (TMP) 4 (O)], 3 in d 6 -benzene. Figure S7. 1 H NOESY NMR spectrum of [Na 2 Mg 2 (TMP) 4 (O)], 3 in d 6 -benzene. nature chemistry 7

8 supplementary information ppm Figure S8. 1 H NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 6 - benzene ppm Figure S9. 1 H NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 8 - THF. 8 nature chemistry

9 supplementary information ppm Figure S C NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 8 -THF ppm Figure S11. 1 H NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 D 4 }], 5(d 4 ) in d 6 -benzene. nature chemistry 9

10 supplementary information ppm Figure S12. 2 H NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 D 4 }], 5(d 4 ) in benzene ppm Figure S13. Comparison of 1 H NMR spectra of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 (upper spectrum) and [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 D 4 }], 5(d 4 ) (lower spectrum) in d 6 -benzene. 10 nature chemistry

11 supplementary information ppm ppm Figure S14. 1 H NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5, hydrolysed with D 2 O to produce C 4 H 4 D 2 in d 6 -benzene. Figure S15. 1 H EXSY NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 in d 6 -benzene. nature chemistry 11

12 supplementary information Figure S16. 1 H EXSY NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 in d 6 -benzene, detail of the aliphatic region. Figure S17. 1 H EXSY NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 in d 6 -benzene, detail of the aromatic region. 12 nature chemistry

13 supplementary information Figure S18. 1 H NOESY NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 in d 6 -benzene. Figure S19. 1 H NOESY NMR spectrum of [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 - C 4 H 4 }], 5 in d 6 -benzene, detail of the aliphatic region. nature chemistry 13

14 supplementary information Figure S20. 1 H EXSY NMR spectrum of a mixture of [Na 2 Mg 2 (TMP) 4 (O)], 3 [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 6 -benzene. and Figure S21. 1 H NOESY NMR spectrum of a mixture of [Na 2 Mg 2 (TMP) 4 (O)], 3 [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 6 -benzene. and 14 nature chemistry

15 supplementary information Figure S22. 1 H NOESY NMR spectrum of a mixture of [Na 2 Mg 2 (TMP) 4 (O)], 3 and [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 6 -benzene, detail of the aliphatic region. Figure S23. 1 H NOESY NMR spectrum of a mixture of [Na 2 Mg 2 (TMP) 4 (O)], 3 and [{(TMEDA)Na(μ-TMP)} 2 {1,4-[Mg(TMP)] 2 -C 4 H 4 }], 5 in d 6 -benzene, detail of the aliphatic region. nature chemistry 15

16 supplementary information References [1] Andersen, R. A. & Wilkinson, G. Bis(neopentyl)-, bis(trimethylsilylmethyl)- and bis(2- methyl-2-phenylpropyl)-magnesium. J. Chem. Soc., Dalton Trans (1977). [2] Andersen, R. A., Carmona-Guzman, E., Gibson, J. F. & Wilkinson, G. Neopentyl, neophyl, and trimethylsilylmethyl compounds of manganese. Manganese(II) dialkyls; manganese(ii) dialkyl amine adducts; tetra-alkylmanganate(ii) ions and lithium salts; manganese(iv) tetra-alkyls. J. Chem. Soc., Dalton Trans (1976). [3] Alberola, A. et al. Bis[(trimethylsilyl)methyl]manganese: Structural variations of its solvent-free and TMEDA-, pyridine-, and dioxane-complexed forms. Organometallics, 28, (2009). [4] Sheldrick, G. M. A short history of SHELX. Acta Cryst. A, 64, (2008). 16 nature chemistry