Synthesis of molybdenum arene complexes containing amide-derived heterodifunctional P,O ligands

Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand

“…In addition, the resonance due to the quaternary carbon atom of the 2,6-diisopropylphenyl in the 13 C{ 1 H} spectrum of 4 shows a carbon-phosphorus coupling of 6 Hz that is not observed in the spectra of phosphinitoimine complexes. This coupling, also observed in related complexes, 57 points out the proximity of the nitrogen-bound carbon and the 31 P nuclei and therefore can be regarded as a fingerprint for the phosphinoamide structure.…”

New Staudinger Strategy Enabled N -Acyl Phosphinamidites Synthesis

“…It's worth to note that 3oa has been used as a multidentate ligand to coordinate with [PtCl 2 (cod)] and [(C 3 H 5 )PdCl] 2 and form metal complexes. 45 Based on previous reports, amidophosphine compounds could potentially serve as novel P, O ligands, [12][13][14][15] this driven us to further explore the possibility of accessing enantiopure variation (Scheme 4). Utilizing wellestablished methods to access chiral azide substrates from corresponding amines, we were able to obtain various of enantiopure amidophosphine products under our condition.…”

“…Since only limited number of reports studied the amidophosphine compound, [12][13][14][15] we then carried out the stability test of 3aa, to collect more information for this type of molecular (Scheme 2b). Initially, we thought 3aa is sensitive to oxygen and water, since during the reaction optimization we found 3aa was obtained in diminished yields when reaction was carried out under air or had additional water.…”

“…[6][7][8] Amidophosphorus (P (v) ) species which contain an N-P bond have been well studied in both synthetic approaches and practical application, and they have been demonstrated to be a valuable class of multi-functional molecules. [9][10][11] In sharp contrast to this, research into N-acyl phosphinamidite (P (III) ) is significantly less developed, and until now this type molecule was limited to serving as a type of hemilabile P,O chelating ligand [12][13][14][15] or as an intermediate in the conversion of sulfonamides to free amines and carbamates (a, Scheme 1). 16 The lack of mild approaches to a diverse range of N-acyl phosphinamidite derivatives is likely to be the factor which has hampered the research into N-acyl phosphinamidites.…”

Monocyclopentadienyl complexes of niobium, tantalum and tungsten containing heterodifunctional P,O ligandsDedicated to Prof. P. Royo on the occasion of his 65th birthday, with our warmest congratulations.

“…More recently, we have described the synthesis of Z-arene-molybdenum complexes, such as [(Z-C 6 H 5 R)Mo(Z-C 3 H 5 ){Ph 2 PXHC(O)R 0 -k 2 P,O}]-[PF 6 ] (R ¼ H, Me; R 0 ¼ Ph, NPh 2 , Me; X ¼ N, C). 22,23 In these complexes, the P,O ligands act either as P-monodentate phosphine or as a P,O-chelate, whereas O-monocoordination, which may have been anticipated owing to the relatively hard nature of molybdenum vs. late transition metals, was not observed. Although ligands with carbonyl functions (ketones, [24][25][26] amides, 27,28 acids/esters 29,30 ) are known to coordinate readily to groups 5 and 6 metals, there has been no example reported, to the best of our knowledge, when a phosphine donor is also present in the ligand.…”