Coordination of P(X)-modified (X=O, S) N-aryl-carbamoylmethylphosphine oxides and sulfides with Pd(II) and Re(I) ions: Facile formation of 6,6-membered pincer complexes featuring atropisomerism

5,6‐ and 6,6‐Membered Palladium(II) Pincer Complexes Based on Functionalized Carboxamides with Ancillary Sulfur and Nitrogen Donors

“…Dichloromethane was distilled from P 2 O 5 . 2‐(Diphenylthiophosphoryl)aniline was obtained from 2‐diphenylphosphinoaniline according to the literature procedure . 2‐(Methylsulfanyl)benzoyl chloride was synthesized from thiosalicylic acid through methylation with MeI followed by treatment with SOCl 2 .…”

“…At the same time, growing attention is focused on various nonclassical hybrid (unsymmetrical) derivatives, as they can combine the properties of symmetrical prototypes or exhibit unique features . Recently, we have shown that multidentate ligands with a secondary amide central unit bearing P=X (X = S and/or O) ancillary donor groups, obtained from o ‐(thio)phosphorylated aniline and (thio)phosphorylacetic acid derivatives, readily undergo cyclometalation upon reaction with PdCl 2 (NCPh) 2 under mild conditions to afford pincer‐type palladium(II) complexes with two six‐membered fused metallocycles . Note that only a limited number of 6,6‐membered pincer complexes have been reported to date .…”

Synthesis, polarity, and structure of 2-chloro-N-[2-(methylsulfanyl)phenyl]- and 2-(diphenylthiophosphoryl)-N-[2-(methylsulfanyl)phenyl]acetamides

“…2-(Methylsulfanyl)aniline was commercial product (Aldrich). Compounds 1 and 2 were synthesized according to procedures analogous to those reported by us previously [3].…”

“…Less common thiophosphoryl analogs of (carbamoylmethyl)phosphine oxides [2], as well as P(X)-modified (carbamoylmethyl)phosphine oxides and sulfides having a third coordination site (e.g., P=S group) [3], are more appropriate ligand for the complexation and purification of thiophiles (Ag, Pd, Pt, etc.). We have synthesized a new complexing agent of this sort, a thiophosphoryl analog of (arylcarbamoylmethyl)phosphine oxides having a methylsulfanyl group in the benzene ring, and studied its structure in solution.…”

Conformational Analysis of N-Alkyl-N-[2-(diphenylphosphoryl)ethyl]amides of Diphenylphosphorylacetic Acid: Dipole Moments, IR Spectroscopy, DFT Study

“…The literature contains data on the structure of complexes of CMPO with rare earth elements and actinides [ 17 , 29 , 30 ], manganese (II) [ 27 ], and mercury (II) [ 31 ] in the solid state. The crystal structures of (diethylcarbamoyl)methyldiphenylphosphine oxide and its protonated form [ 32 ], diphenylmorpholine carbamoylmethyl phosphine oxide [ 33 ], diphenyl- N , N -dimethylcarbamoylmethylphosphine oxide [ 34 ], N -aryl-substituted CMPO modified with a phosphoryl group, and its complexes with Pd (II) and Re (I) [ 35 ] were determined by X-ray diffraction. Information on the structure in solution is available only for P(X)-modified (X = O, S) N -aryl-substituted CMPOs: experimental and theoretical conformational analysis by the methods of dipole moments and quantum chemistry showed that in solution, these compounds exist as an equilibrium of several conformers with intramolecular hydrogen bonds H⋯X [ 36 ].…”