A comparison of NH3, PH3, PH2, OH2 and SH as ligands in iridium(III) complexes

Hydrolytic disproportionation of coordinated white phosphorus in [CpRu(dppe)(η1-P4)]PF6 [dppe=1,2-bis(diphenylphosphino)ethane]

“…The latter resonances exhibit a large coupling (1137 Hz), which is typical for a P-F group, and a small one due to the coupling with the dppe phosphorus donors. The 31 P and 19 F NMR spectra exhibit also the resonances due to the PF 2 O À 2 anion [31]. The behaviour of the coordinated P(OH) 3 in the present dppe derivative 6 parallels that of the same ligand in the [CpRu(PPh 3 ) 2 {P(OH) 3 }]PF 6 compound (9) [23], which yields the [CpRu(PPh 3 ) 2 {P-F(OH) 2 }]PF 2 O 2 product (10) by decomposition [23], showing that the hexafluorophosphate hydrolysis leads to substitution of an OH of the coordinated P(OH) 3 ligand by a fluorine atom, to yield the PF(OH) 2 species which is the tautomer of the extremely unstable monofluorophosphorous acid, HPFO(OH), detected only in small amounts in the reactions of HPF 2 O [32].…”

“…The complex, which adds to the small group of metal PH 3 derivatives [1, [16][17][18][19][20][21][22], is quite stable under an inert atmosphere and the PH 3 molecule remains firmly coordinated to the metal in solution, yielding a first-order A 2 C spin pattern in the 31 P NMR spectrum; the lower field doublet is assigned to the phosphorus atoms (P A ) of the dppe ligand and the higher field triplet to the phosphine atom (P C ). The latter signal turns into a quartet of triplets in the 31 P-1 H coupled spectrum, the observed value of 1 J(P-H) (360.0 Hz) being in the range of those found for the [CpRu(PPh 3 ) 2 (PH 3 )]Y complexes (Y = PF 6 , CF 3 SO 3 ) [1] and for tetracoordinated P-H systems [12].…”

“…The solvents were purified according to standard procedures [33]. The 1 H, 19 [CpRu(dppe)Cl] (1) was prepared according to the literature method [34]. H 3 PO 2 and H 3 PO 3 water solutions and the ligand dppe (Aldrich) were used as received.…”

Intramolecular Metal Ligand Aromatic Cation−π Interactions in Crystal Structures of Transition Metal Complexes

“…Hence, it is not possible to observe a regular correlation between the interaction distances and the amount of positive charge on the hydrogen atom, as is possible with metalloproteins where MLACπ interactions are not as constrained by steric influences. [23] It is interesting to point out that from spectra of the trans,mer-[IrCl 2 (NH 3 )(PMe 2 Ph) 3 ] ϩ complex in solution, it is evident that there is rapid rotation about the IrϪP bonds, [45] which means that there are no MLACπ interactions in solution.…”

Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex

“…[Ir(CO)(H)(L) 2 X(PH 2 )] 21 (L = PEt 3 , ½ dppe; X = Br, Cl), [IrCl 2 (PMe 2 Ph) 3 (PH 2 )], 22 and two recent examples with fac-L 3 -iridium(I) 23 and mer-L 3 -iridium(III) 24 scaffolds in which the phosphanido functionality is embedded within a tripodal ligand.…”