Formation of a Palladium Thioketone Complex from a Thiophosphinoyl Stabilized Li/Cl Carbenoid

Substitution Effects on the Formation of T‐Shaped Palladium Carbene and Thioketone Complexes from Li/Cl Carbenoids

“…For computational cost we first chose a model system with PPh 3 replaced by PH 3 ligands. After our preliminary investigations on the trimethylsilyl‐substituted carbenoid, we suggested a kind of rearrangement leading directly from the carbene complex 9 a – PPh 3 to thioketone 8 a 9. The latter would be formed selectively due to thermodynamic reasons.…”

“…After our preliminary investigations on the trimethylsilyl-substituted carbenoid, we suggested a kind of rearrangement leading directly from the carbene complex 9 a-PPh 3 to thioketone 8 a. [9] The latter would be formed selectively due to thermodynamic reasons. However, calculations show that there is no low-energy pathway leading directly from the carbene to the thioketone complex.…”

“…They employed lithium chloride carbenoid 1 to access palladium complex 2 , which had earlier been prepared from the corresponding dilithio methandiide (Figure 2). 8 To extend the applicability of this approach also on carbenoids with other substituents than P V moieties we have recently reported on the silyl derivative 3 9. This carbenoid, however, selectively reacted with [Pd(PPh 3 ) 4 ] under formation of the palladium thioketone 4 .…”

“…[8] To [a] S. Molitor, K.-S. Feichtner, C. Kupper, Dr. V. H. Gessner Institut für Anorganische Chemie Julius-Maximilians-Universität Würzburg Am Hubland, 97074 Würzburg (Germany) E-mail: vgessner@uni-wuerzburg.de extend the applicability of this approach also on carbenoids with other substituents than P V moieties we have recently reported on the silyl derivative 3. [9] This carbenoid, however, selectively reacted with [Pd(PPh 3 ) 4 ] under formation of the palladium thioketone 4. In this case, no formation of a carbene complex was observed.…”

Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners

“…Ar 2 PPAr 2 ,with Ar = p-MeC 6 H 4 ), thus confirming their ambiphilic nature and their ability to eliminate MCl (see the Supporting Information for details). [28] Thus,t his transformation offers an excellent model reaction to examine the stability-reactivity relationship of compound series 1-M.F ortunately,t reatment of sodium or potassium carbenoid, 1-Na or 1-K,with 1equiv [Pd(PPh 3 ) 4 ]i nT HF at RT provided selective access to carbene complex 3,w ith no thioketone formation observed. [9,27] However,t his method has often been limited by side-reactions associated with the high reactivity and low stability of carbenoids.…”