Umsetzung von Ph₃P=C=PPh₃ mit Lewis‐Säuren von Hauptgruppenelementen; Synthesen, Strukturen und Reaktionen der Additionsverbindungen [Br₃Al{C(PPh₃)₂}] und [Me₃In{C(PPh₃)₂}]

Abstract

Die Umsetzung des Carbodiphosphorans Ph3P=C=PPh3 (1) mit InMe3 in THF und von AlBr3 in Toluol liefert die Addukte [Me3In{C(PPh3)2}] (2) und [Br3Al{C(PPh3)2}] (3) mit sehr guten Ausbeuten. 1 reagiert nicht mit SnCl2 und Me3SnCl; als Nebenprodukt konnten jedoch geringe Mengen des Hydrolyseprodukts [HC(PPh3)2][Me3SnCl2] (6) als Einkristalle erhalten werden. 2 löst sich in HCCl3 unter Bildung der Salze [HC(PPh3)2][MeInCl3] (5a) und [HC(PPh3)2][Me2InCl2] (5b). Wenige Kristalle von [HC(PPh3)2][Me2In(OSiMe2OSiMe2O)] (4) wurden als Reaktionsprodukt von 2 mit dem Silikon‐Schliffett bei Kristallisationsversuchen von 2 erhalten. Beim Versuch, 2 mit CS2 in THF umzusetzen wurde das THF‐Spaltungsprodukt [HC(PPh3)2][CH3CH2CH2OCS2] (7) in 60 %iger Ausbeute erhalten. Sämtliche Verbindungen wurden durch Einkristallstrukturanalysen charakterisiert, inklusive das bei der Darstellung von 3 angefallene Nebenprodukt [Br3Al{OP(C6H5)2CH2P(C6H5)3}][AlBr4] (8) sowie die zur Synthese von 1 verwendete salzartige Verbindung [ClC(PPh3)2]Cl (9).

Divalent Carbon(0) Chemistry, Part 2: Protonation and Complexes with Main Group and Transition Metal Lewis Acids

“…[26] Experimental values have also been reported for the protonated compounds 3-H + , [27] 9-H + [28] and for the diprotonated species 2-(H + ) 2 [29] and 3-(H + ) 2 , [30] as well as for substituted analogues of 7-H + , [31] 8-H + [32] and 8-(H + ) 2 .…”

“…Preliminary calculations support this assumption. [36] Complexes 3-AlBr 3 [37] and 9-AlR 3 (R = Cl, H, Me with different substitution patterns at the NHC ring) [38,39] have already been isolated and characterized.…”

Reaction of Double Ylide C(PPh3)2 with [W(CO)6] – Crystal Structures of [(CO)5­W(CCPPh3)] and [(CO)5W{η1‐O2C2(PPh3)2}] and Bonding Analyses of [TM­(CCPR3)] Compounds

“…Such a complex would exhibit a pair of doublet signals in the 31 P NMR spectrum according to nonequivalent phosphorus atoms, and we believe that this adduct is not the result of the action of water on [(CO) 5 5 W-(C{PPh 3 } 2 )] was described and a signal at δ = 20.7 ppm in the 31 P NMR spectrum was assigned to this complex; [3] however, we believe that this signal is due to cation (Hǟ1) + , because this value is typical for (Hǟ1)X salts. [9] To avoid potential proton donors such as thf, CH 2 Cl 2 , dme, or dmso, we studied the reaction of 1 with [W(CO) 6 ] in benzene. At room temperature, no reaction was observed, as shown by monitoring the progress of the reaction by 31 P NMR spectroscopy.…”

“…∆E (= -D e ) = ∆E int + ∆E prep (9) Further details on the EDA method and its application to the analysis of the chemical bond [59] can be found in the literature.…”

“…[5] Similar Rh I and Rh III complexes have also been described. [6] Further compounds of the type Mǟ1, in which M are main group [7][8][9] or transition metal Lewis acids, [10][11][12] can be found in the literature.…”