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Experimental Section

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Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands

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Abstract

All experiments were carried out in an argon atmosphere under strict exclusion of oxygen and moisture using Schlenk or glove box techniques.

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Notes

  1. 1.

    G. M. Sheldrick, SHELXS97 and SHELXL97, University of Göttingen, Germany, 1997.

  2. 2.

    The preparation of sodium naphthalenide solution in THF from sodium and naphthalene has been reported: H. C. Wang, G. Levin, M. Szwarc, J. Am. Chem. Soc. 1978, 100, 3969.

  3. 3.

    A very small amount of Tp′Mo(CO)2PMe3 (2-Mo) was always observed as an intermediate during addition. After addition was completed, the IR spectrum of the solution showed only ν(CO) bands of the metalate 3-Mo.

  4. 4.

    Complex 6-Mo is overall Cs-symmetric in solution. The coordination plane of the zwitterionic silylidene ligand defined by the atoms W, Si, CTbb and N4-dmap lies in the symmetry plane of the molecule, which also contains the pyridine ring plane of 4-dmap, whereas the aryl ring plane of the Tbb substituent lies orthogonal to the symmetry plane. This renders the two ortho CH(TMS)2 groups enantiotopic. Due to hindered rotation of the Tbb substituent about the Si-CTbb bond the two TMS groups in each CH(TMS)2 group are diastereotopic and give rise to two separate signals in the NMR spectra at low temperature. The most shielded TMS group in the 1H NMR spectrum was labeled with the character A and the other TMS group with the character B. The corresponding 13C signals were assigned by an HMQC experiment.

  5. 5.

    The C2,6-H signal of 4-dmap could not be detected at 298 K due to broadening.

  6. 6.

    Complex 6-W is overall Cs-symmetric in solution. The coordination plane of the zwitterionic silylidene ligand defined by the atoms W, Si, CTbb and N4-dmap lies in the symmetry plane of the molecule, which also contains the pyridine ring plane of 4-dmap, whereas the aryl ring plane of the Tbb substituent lies orthogonal to the symmetry plane. This renders the two ortho CH(TMS)2 groups enantiotopic. Due to hindered rotation of the Tbb substituent about the Si-CTbb bond the two TMS groups in each CH(TMS)2 group are diastereotopic and give rise to two separate signals in the NMR spectra at low temperature. The most shielded TMS group in the 1H NMR spectrum was labeled with the character A and the other TMS group with the character B. The corresponding 13C signals were assigned by an HMQC experiment. Similarly, hindered rotation of the 4-dmap group about the Si-N bond renders the C2 and C6, and the C3 and C5 positions of the pyridine ring chemically inequivalent and gives rise to four 1H and 13C NMR signals at low temperature. Using HMQC and HMBC experiments all signals could be unequivocally assigned. The most shielded signal in the 1H NMR spectrum at δ = 6.17 ppm was taken as the C3-H group.

  7. 7.

    The C2,6-H signal of 4-dmap could not be detected at 298 K due to broadening.

  8. 8.

    The composition of the diethylether solvate of 21-Mo was determined by 1H NMR spectroscopy.

  9. 9.

    The signal of MesNC was not observed in the 13{1H} NMR spectrum.

  10. 10.

    Two different Tp′ ligands on two molybdenum center can’t be differentiate from correlation spectra.

  11. 11.

    Two different Tp′ ligands on two molybdenum center can’t be differentiate from correlation spectra.

  12. 12.

    One set of CO signal is not visible because of very broadness. Some signals appear as a very broad and the Δν1/2 can’t be determine because of either overlap with other signals or because of lack of proper shape of the signal.

  13. 13.

    This signal partially overlaps with the signal at 15.52 ppm.

  14. 14.

    Only some [(η5-C5H4Me)Mn(CO)3] was additionally formed (ν(CO) in fluorobenzene: 2019 (s) and 1930 (vs) cm−1) probably by photodegradation of 35 or the dichloroplumbyl complex.

  15. 15.

    1 equiv. of Na[B(C6H3-3,5-(CF3)2)4] was used to get the corresponding plumbylidyne complex but the reaction leads to the formation of bridging complex 38. Later on, it was found that this bridging complex 38 very slowly converted to the corresponding plumbylidyne complex upon storing a fluorobenzene/n-pentane solution at −30 °C for several months (>2 months).

  16. 16.

    The ν(CO) bands of the intermediate product compare well with those of the analogous bromo-bridged complex [{(η5-C5H4Me)(CO)2MnPb(C6H3-2,6-Mes2)}2(μ-Br)][B{C6H3-3,5-(CF3)2}4], which is selectively formed in the reaction of [(η5-C5H4Me)(CO)2Mn = Pb(C6H3-2,6-Mes2)Br] with Na[B{C6H3-3,5-(CF3)2}4]. The latter compound was isolated as an analytically pure brown solid that was characterized by IR spectroscopy, 1H NMR and 13C NMR spectroscopy, and single-crystal X ray-diffraction.

  17. 17.

    The signals marked with an asterisk correspond to an AB2 spin system showing a small second-order splitting of the doublet and the triplet signal, respectively. The given 3J(H,H) coupling constant of 7.8 Hz was confirmed by simulation with the program gNMR (gNMR, Version 5.0.6.0, P. H. M. Budzelaar, IvorySoft, Centennial, USA, 2006).

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  1. Institute für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Bonn, Nordrhein-Westfalen, Germany

    Priyabrata Ghana

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Ghana, P. (2019). Experimental Section. In: Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-02625-7_13

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