Thf d8

All reactions
and product manipulations
were performed under an inert atmosphere of argon or dinitrogen by
using standard Schlenk-line or glovebox techniques (MBraun UNIlab
glovebox maintained at <0.1 ppm of H₂O and <0.1 ppm
of O₂). Generation of ⁱPr₃SiOCP was adapted from the previously reported synthesis.^{23 (link)} Na[PCO(dioxane)_5.6],^{38 (link)} [Mg(^DippNacNac)]₂,^{39 (link)} IMes,^{40 (link)} IⁱPr,^{41 (link)} [Ge(^DippNacNac)Cl],^{42 (link)} [Sn(^DippNacNac)Cl],^{42 (link)} [(IDipp)AuCl],^{35 (link)} and [Co(^DippPDI)Cl]^{43 (link)} were synthesized according
to previously reported synthetic procedures. Triisopropylsilyl trifluoromethanesulfonate
(Sigma-Aldrich) and chlorotrimethylsilane (Sigma-Aldrich) were
used as received. Hexane (hex; Sigma-Aldrich, HPLC grade) and toluene
(Sigma-Aldrich, HPLC grade) were purified by using an MBraun SPS-800
solvent system. C₆D₆ (Aldrich, 99.5%) was dried
over CaH₂ and degassed prior to use. THF (Sigma-Aldrich,
HPLC grade) and THF-d₈ (Sigma-Aldrich,
99.5%) were distilled over sodium/benzophenone. All dry solvents were
stored under argon in gastight ampules. Additionally, solvents were
stored over activated 3 Å molecular sieves.

Cu(acac)₂ (Copper(II) acetylacetonate, 97%), dimethylamine-borane complex (DMAB, Me₂NHBH_3, 97%), carbon disulfide (CS₂, ≥99%), THF-d_8, and hexane (99%) were bought from Sigma-Aldrich. Ethanol was bought from Merck. Acetone was used to clean all glass materials and Teflon-coated magnetic stir bars. All materials were rinsed a few times with copious amounts of distilled water and then dried at high temperature (110°C) in the oven during the night.

Unless stated otherwise, all of
the experiments were conducted
using standard Schlenk line and glovebox techniques under an inert
atmosphere of argon. NMR spectra were recorded with a Bruker AVANCE
III spectrometer (¹H at 400 MHz; ¹³C at 101
MHz). The spectra are referenced relative to residual protio solvent
resonances. Elemental analyses were performed at Elemental Microanalysis
Ltd., Okehampton, Devon, UK. Solvents were dried by passage through
a commercially available solvent purification system and stored under
argon in ampoules over 4 Å molecular sieves. Benzene-d₆ and THF-d₈ were
purchased from Sigma-Aldrich and dried over a potassium mirror before
distilling and storage over molecular sieves. [{SiN^Dipp}AlI] (13) and [{SiN^Dipp}AlK]₂ (12) were prepared according to the reported procedures.^{29 (link)} All other chemicals were purchased from Merck
and used without further purification.