Facile preparation of trimethylsilylphosphaalkyne and its conversion to polyphospholide anions

Access to 1,2,3-triphospholide ligands by reduction of di-tert-butyldiphosphatetrahedrane

“…In contrast, the reduction chemistry of the closely-related compounds P 4 ( E ) and tert -butylphosphaalkyne ( t BuCP, the monomer of A ) is well-investigated. 15–19 Reactions of P 4 with sodium afford pentaphospholide, tetraphospholide and 1,2,3-triphospholide anions (among other polyphosphide species), 15,16 while reduction of phosphaalkynes (RCP) with Na/Hg (and other alkali metal reductands) yields di- and 1,2,4-triphospholides. 17–19 These previous results inspired us to explore similar reductions of ( t BuCP) 2 ( A ) (Fig.…”

η1:η2-P-Pyrazolylphosphaalkene Complexes of Ruthenium(0)

“…The same approach has typically been cited in the development of kinetically stabilized phosphaalkynes (e.g., t BuC≡P, AdC≡P), however, in these cases the bulk is often sufficiently remote from the reactive π-system as to preclude it being the sole stabilizing influence. Moreover, even bulky phosphaalkynes, e.g., R 3 SiC≡P (R = Ph [9], Me [10,11]) often exhibit only limited stability, in some instances comparable to that of unencumbered systems (e.g., MeC≡P [12]). Significantly, the formally related phosphaethynyloate ion "O-C≡P − " is isolable as a sodium salt [13,14], which exhibits appreciable stability despite the lack of any steric "protection"; this fact is attributed to electronic influences, with alongside computational studies of the isolated cyaphide ion ("C≡P − "), which indicate an intrinsically unstable hypovalent "[C=P] − " structure [15], this would imply that electronics serve an equally important role in imparting stability to low-coordinate phosphacarbons.…”

Photochemical C(sp)C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnMCP

“…Details of the data quality and a summary of the residual values of the refinements are listed in tables 2,4,6,8,10,and 12 below. Tables 3,5,7,9,11 and 13 give all bond lengths and angles for the five structures.…”

“…The n-pentane was removed by reduced pressure, yielding a colorless powder (543 mg, 1.88 mmol, 31%). 2,4,6-triisopropylphenylphosphaalkyne (2) and 2,4,6-trimethylphenylphosphaalkyne (3) were prepared using a modified literature procedure [9] via a three step synthesis. Reaction details are given in the specific section for those compounds.…”

“…AgOTf (2.54 g, 9.87 mmol, 2.1 eq) was added into a toluene solution (100 mL) of 2b (1.50 g, 4.70 mmol, 1.0 eq) and stirred for 30 min at rt. After the addition of 1,4-diazabicyclo[2.2.2]octane (DABCO,1.11 g,9.87 mmol, 2.1 eq) the reaction mixture was stirred at 50 °C for 1 h. The four reaction mixtures were combined and filtered through diatomaceous earth to remove the AgCl.…”