Preparation and crystal structure of [HPPh2NH-p-tolyl)]-[Rh(COD)Cl2]. A rhodium(I) complex containing a new σ-N,σ-C-chelating iminophosphoranylmethanide ligand

Preparation and properties of rhodium(I) and iridium(I) diolefin complexes of heterodifunctional phosphorus–imine chelating ligands and a related iminophosphine. 103Rh NMR parameters of the rhodium complexes obtained via indirect two-dimensional 31P, 103Rh{1H} NMR spectroscopy

“…There are, however, only a few examples of rhodium complexes containing chelating ligands with both a phosphine and an imine donor site (36)(37)(38)(39). There are no examples of cationic rhodium(1) or iridium(1) complexes of phosphoranimine-phosphine heterodifunctional ligands such as those described herein, although the work of Irnhoff et al (40)(41)(42)(43) provides several examples of cationic complexes containing doubly oxidized iminophosphorane ligands acting as bidentate ligands to Ir and Rh through the nitrogen atoms or through one nitrogen and one carbon atom.…”

A new and convenient approach towards bis(iminophosphoranyl)methane ligands and their dicationic, cationic, anionic and dianionic derivatives

“…In 1990s, Elsevier and coworkers observed a (1,3) shift of a proton (from the methylene group to one nitrogen atom) during their studies on the coordination behavior of the bis(iminophosphorane) derivative [(ArNPQPh 2 )CH 2 ] (Ar ¼ p-Me-C 6 H 4 ) with rhodium and platinum precursors. 11,[47][48][49][50][51] Complexes resulting from coordination of the bis(iminophosphorane) tautomeric form were characterized in the crude reaction mixture by NMR techniques but not isolated. On the basis of this and our own results, one may conclude that the electron donating capacity of the substituent at nitrogen is the predominant factor in the (1,3) hydrogen shift.…”

“…Bis(iminophosphorane)methane ligands are most interesting species because of their potential chelating behavior. [11][12][13][14] Furthermore, the presence of two acidic protons at the methylene bridge offers the possibility to generate anionic derivatives which are structurally related to acetylacetonates and b-diketiminates, and even geminal dianions via double deprotonation. [15][16][17] This was nicely illustrated by Cavell and coworkers who have studied the coordination chemistry of such a dianionic derivative (N-TMS) with lanthanides and transition metals.…”

Coordination Chemistry and Diphenylacetylene Hydrogenation Catalysis of Planar Chiral Ferrocenylphosphane‐Thioether Ligands with Cyclooctadieneiridium(I)

“…Indentification of such an interaction in solution by NMR spectroscopy was precluded by the complex redistribution equilibria (see below). However, the Ir atom in each ion sits very close to the ideal square place defined by the middle of the C=C bonds and the P,S or Cl donors, respectively [0.0158 (5) [61][62][63][64][65] Selected bonding parameters for compounds 3-Ph are shown in Table 4. Both ions exhibit a relatively undistorted …”