94477-72-2Relevant academic research and scientific papers
Diaminocarbene and phosphonium ylide ligands: A systematic comparison of their donor character
Canac, Yves,Lepetit, Christine,Abdalilah, Mohammed,Duhayon, Carine,Chauvin, Remi
experimental part, p. 8406 - 8413 (2009/02/02)
The coordinating properties of the diaminocarbene (A) and phosphonium ylide (B) ligand types have been investigated systematically through a test family of C,C-chelating ligands containing two moieties of either kind. The overall character of o-C6H4AaBb ligands (a + b = 2) has been analyzed from the IR CO stretching frequencies of isostructural complexes [(η2-C6H4AaB b)Rh(CO)2][TfO]. The test moieties A = NC 2H2N+(Me)C- and B = Ph 2P+CH2- were first considered. While the ligands bearing at least one diaminocarbene end (AA, a = 2 and AB, a = 1) could be generated (and trapped by complexation), the bis-ylide case BB (a = 0) proved to be awkward: treatment of the dication C6H 4(P+Ph2Me)2 with n-BuLi indeed lead to the Schmidbaur's carbodiphosphorane Ph3P=C=PPh2Me, through an unprecendented ylidopentacoordinated phosphorane which could be fully characterized by NMR techniques. The bis-ylide ligand type C6H 4B2 could however be generated by bridging the phosphonium methyl groups by a methylene link (B2 = (P+Ph 2CH-)2CH2), preventing the formation of the analogous highly strained carbodiphosphorane. The three complexes [(η2-C6H4AaBb)Rh(CO) 2][TfO] were fully characterized, including by X-ray diffraction analysis and 103Rh NMR spectroscopy. Comparison of their IR spectra indicated that the A2 type bis-NHC ligand is less donating than the hybrid AB type, which is itself less donating than the B2 type bis-ylide ligand. The excellent linear variation of the νCO frequencies vs a (= 0, 1, 2) shows that the coordinating moieties act in a pseudoindependent way. This was confirmed by DFT calculations at the B3PW91/6-31G**/LANL2DZ*(Rh) level. It is therefore demonstrated that a phosphonium ylide ligand is a stronger donor than a diaminocarbene ligand.
Preparation of Unsymmetrical Methyl/Phenylcarbodiphosphoranes Through Stepwise Synthesis or Rearrangement
Schmidbaur, Hubert,Herr, Rudolf,Zybill, Christian E.
, p. 3374 - 3380 (2007/10/02)
The bis-phosphonium salt 1,2-C6H4(PPh2Me+SO3F-)2 (8), obtained from the double quaternisation of 1,2-bis(diphenylphosphino)benzene (6) using CH3OSO2F, yields on transylidation with excess Et3P=CHMe as an unexpected rearrangement prod
