Transition metal complexes with bidentate ligands spanning trans ‐positions. IV. Preparation and properties of some rhodium and iridium complexes of 2,11‐bis(diphenylphosphinomethyl)benzo [ c ]phenanthrene
1977; Wiley; Volume: 60; Issue: 8 Linguagem: Inglês
10.1002/hlca.19770600833
ISSN1522-2675
AutoresF. J. S. Reed, Luigi M. Venanzi,
Tópico(s)Asymmetric Hydrogenation and Catalysis
ResumoAbstract The bidentate phosphine 2,11‐bis(diphenylphosphinomethyl)benzo [ c ]phenanthrene ( 1 ) has been used to prepare the mononuclear, square planar complexes trans ‐[MX(CO)( 1 )] and trans ‐[M(CO)(CH 3 CN)( 1 )][BF 4 ] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O 2 and SO 2 is significantly lower than that of the corresponding Ph 3 P complexes. The oxidative‐addition reactions of complexes trans ‐[IrX (CO) ( 1 )] with hydrogen halides give the six‐coordinate species [IrHX 2 (CO) ( 1 )]. The complexes [IrH 2 I (CO) ( 1 )] and [IrH 2 L (CO) ( 1 )] [BF 4 ] (L = CO and CH 3 CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans ‐[MCl (CO) (Ph 2 PCH 2 Ph) 2 ] (M = Rh, Ir), trans ‐[Ir (CO) (CH 3 CN) (Ph 2 PCH 2 Ph) 2 ] [BF 4 ], [IrHCl 2 (CO)(Ph 2 PCH 2 Ph) 2 ] and [IrH 2 (CO) 2 (Ph 2 PCH 2 Ph) 2 ] [BF 4 ] have been prepared and their special parameters are compared with those of the corresponding complexes of ligand 1 . The influence of the static requirements of this ligand on the chemistry of its rhodium and iridium complexes is discussed.
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