690634-60-7Relevant academic research and scientific papers
Synthesis, structure, reactivity, and catalytic activity of C,N- and C,N,N-orthopalladated iminophosphoranes
Bielsa, Raquel,Larrea, Angel,Navarro, Rafael,Soler, Tatiana,Urriolabeitia, Esteban P.
, p. 1724 - 1736 (2007/10/03)
The orthopalladated complexes [Pd(μ-Cl)(C6H 4-2PPh2=NPh-κ-C,N)]2 (1) and [Pd(C 6H4-2-PPh2=N-C(O)-2NC5H 4-κ-C,N,N)Cl] (11) have been obtained by reaction of Pd(OAc)2 (OAc = acetate) with the iminophosphoranes Ph 3P=NPh and Ph3P=N-C(O)-2-NC5H4, respectively, in the presence of excess LiCl. Complex 11 has been characterised by X-ray diffraction methods. The orthoplatinated derivative [Pt(C 6H4-2-PPh2=N-C(O)-2-NC5H 4-κ-C,N,N)a] (12) can be obtained by reaction of [PtCl 2(NCPh)2] with Ph3P=N-C(O)-2-NC 5H4 in refluxing 2-methoxyethanol. Complex 1 shows the typical reactivity of C,N-orthopalladated complexes, while complex 11 shows that the C,N,N-orthometallated ligand is strongly bonded to the Pd atom and cannot be easily displaced. The catalytic activity of the complexes [Pd(μ-Cl)-(C6H4-2-PPh 2=NPh-κ-C,N)]2 (1), [Pd6(C 6H4-PPh2NPh-κ-C,N)(Cl)(py)] (4), [Pd(C6H4-2-PPh2=N-C(O)-2-NC5H 4-κ-C,N,N)Cl] (11) and [Pd(C6H 4-2-PPh2=N-C(O)-2-NC5H 4-κ-C,N,N)(NCMe)]ClO4 (13) in the Mizoroki-Heck (MH) reaction between methyl acrylate and different haloarenes has been examined. All complexes behave as moderate to good catalysts, yielding turnover numbers (TON) up to 526000. Their role as catalysts or precatalysts and the formation of nanoparticles is also discussed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Metallated triphenylphosphinimine complexes
Wei, Pingrong,Chan, Katie T.K.,Stephan, Douglas W.
, p. 3804 - 3810 (2007/10/03)
The reagent [(o-C6H4PPh2NSiMe3)Li]2 ·Et2O 1 reacted with BCl3 affording (o-C6H4PPh2NSiMe3)BCl2 4. Similarly reaction of 1 with Me2AlCl resulted in a 1:1 mixture of (o-C6H4PPh2NSiMe3)AlMe2 5 and (o-C6H4PPh2NSiMe3)-Al(Me)Cl 6 while the analogous reaction of 1 with GaCl3 gave (o-C6H4PPh2NSiMe3)2 Ga(o-C6H4PPh2NH) 7. The analogous compound [Li(o-C6H4PPh2NPh)]2· Et2O 2 was used to make (o-C6H4PPh2NPh)GaCl2 8, while reaction of 2 with Me2AlCl gave a mixture of [(o-C6H4PPh2NPh)AlCl2] 9 and the salt [(o-C6H4PPh2NPh)2Al] [AlMeCl3] 10. The compound 2 also reacts with PdCl2(COD) affording [Pd(o-C6H4PPh2NPh) (μ-Cl)]2 11 and [Pd(o-C6H4PPh2 NPh)2] 12. Similarly, the complexes [Ni(o-C6H4 PPh2NPh)2] 13 and [Ni(o-C6H4PPh2N(3,5-C6H3 Me2))2] 14 were prepared. The compounds 4-14 have been structurally characterized by X-ray methods.
