We report about the first X-ray structure analyses of the CS2 and CO2 adducts with carbodiphosphorane C(PPh3)2 and the synthesis and X-ray structure analysis of group 6 carbonyl complexes with compound S2CC(PPh3)2 as a ligand [(CO)4MS2CC(PPh3)2] (M = Cr, Mo, W). The nature of the carbon-carbon bonding in X2CC(PPh3)2 and in the model compounds X2CC(PH3)2 and the metal-ligand bonding in [(CO)4MoS2CC(PH3)2] have been analyzed with charge and energy decomposition methods using DFT calculations. Carbodiphosphoranes C(PR3)2 are double electron pair donors having sigma- and pi-carbon lone-pair orbitals as the two highest occupied MOs.
The complex [(cod)PtI 2 ] (cod ) 1,5-cyclooctadiene) reacts with 3 equiv of the hexaphenylcarbodiphosphorane Ph 3 PdCdPPh 3 (1) in THF solution to give the novel Pt(II) complex [(η 3 -C 8 H 11 )Pt(C 6 H 4 PPh 2 CPPh 3 )] (2) along with the salt [HC(PPh 3 ) 2 ]I. In addition to the coordination of the ylidic carbon atom at the Pt atom, 2 contains two further Pt-C σ bonds originating from H to Pt exchange in the ortho position of one phenyl group of the carbodiphosphorane ligand and in the former cod ligand. The resulting C 8 H 11 moiety is coordinated to the Pt atom in an η 3 manner via a double bond and a σ bond and contains a further uncoordinated double bond. From a 1:1 reaction mixture in toluene/CH 2 Cl 2 the majority of the crystals consist of the salt [HC(PPh 3 ) 2 ]I‚2CH 2 Cl 2 (3) with small amounts of platinum compounds as byproducts. The Pt(0) complex [(PPh 3 ) 2 Pt(CH 2 dCH 2 )] does not react with 1 but decomposes at elevated temperatures to give the known dinuclear complex [Pt 2 -(PPh 3 ) 2 (µ-PPh 2 ) 2 ] (4). The complexes 2 and 4 and the salt 3 could be characterized by X-ray analyses and the usual spectroscopic methods.
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).
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