Reactions Of Complexes Trans Research Articles

Cationic Acetyl Complexes of Iron(II) and Ruthenium(II) Bearing Neutral N,O Ligands: Synthesis, Characterization, and Interionic Solution Structure by NOESY NMR Spectroscopy

The reactions of complexes trans, cis-M(PMe3)2(CO)2(Me)I (M = Fe (1a), Ru (1b)) with N,O ligands [2-acetylpyridine (2-apy), 2-benzoylpyridine (2-bzpy), and 2,2‘-dipyridyl ketone (2,2‘-dpk)] in the presence of NaBPh4 afford a mixture of the two possible stereoisomers trans-[M(PMe3)2(CO)(COMe)(N, O)]BPh4 having the N arm cis (A) or trans (B) to the acetyl group. The stereochemistry of the complexes was determined by 1H NOESY NMR spectra. For all the iron complexes the major stereoisomer is B, while for ruthenium complexes it is A. When A/B mixtures are left in methylene chloride, the concentration of A increases, indicating that A and B are the thermodynamic and kinetic reaction products, respectively. Furthermore, the more basic the N,O ligands, the more B stereoisomer that forms. The solid-state structure of 4b was obtained using single-crystal X-ray diffraction. For all the complexes, the ion-pair structures and the localization of the counterion in solution with respect to the organometallic moiety were...

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

AbstractThe 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)(CH3CN)(1)][BF4] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O2 and SO2 is significantly lower than that of the corresponding Ph3P complexes. The oxidative‐addition reactions of complexes trans‐[IrX (CO) (1)] with hydrogen halides give the six‐coordinate species [IrHX2(CO) (1)]. The complexes [IrH2I (CO) (1)] and [IrH2L (CO) (1)] [BF4] (L = CO and CH3CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans‐[MCl (CO) (Ph2PCH2Ph)2] (M = Rh, Ir), trans‐[Ir (CO) (CH3CN) (Ph2PCH2Ph)2] [BF4], [IrHCl2(CO)(Ph2PCH2Ph)2] and [IrH2(CO)2(Ph2PCH2Ph)2] [BF4] 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.