N–H bond activation by palladium(ii) and copper(i) complexes featuring a reactive bidentate PN-ligand

Abstract

The first examples of reactivity at the backbone of a bidentate PN-ligand L1H relevant to N-H activation are described, leading to novel Pd(II) and Cu(I) amido complexes. Activation of the PN-ligand backbone led to selective dearomatization of the pyridyl ring structure. In the case of Pd(II), the intermediate could be efficiently stabilized using PMe(3). Selective N-H bond cleavage of e.g. trifluorosulfonylamide resulted in facile formation of mononuclear metal-amido species 2 and 4, which have been crystallographically characterized. Hydrogen-bonding dimerization is observed in these solid state structures. The results obtained with these structurally versatile and reactive scaffolds likely open up new avenues in cooperative catalysis.

Hemilability of P(X)N-type ligands (X = O, N–H): rollover cyclometalation and benzene C–H activation from (P(X)N)PtMe2complexes

“…The chemistry of the related bifunctional P(N-H)N ligand on platinum was also examined. The tBu P(N-H)N ligand ( tBu P(N-H)N = (di-tert-butylphosphino)-2-aminopyridine) 32 was combined with [PtMe 2 (SMe 2 )] 2 15 in toluene at room temperature to generate ( tBu P(N-H)N)PtMe 2 (3). Complex 3 was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography.…”

Synthesis, Structure, and Characterization of Emissive Neutral Dinuclear CuI Complexes with a Tetraphosphane Bridging Ligand

“…The all‐electron basis set of 6‐31G* was used for other non‐metal atoms of P, N, C, B, and H. Visualization of the optimized structures and frontier molecular orbitals were performed by GaussView. The partition orbital composition was analyzed by using the Multiwfn 2.4 program …”

“…The partition orbital composition was analyzed by using the Multiwfn 2.4 program. [22] Supporting Information (see footnote on the first page of this article): Characterization data and computation data.…”

Iron complexes of a bidentate picolyl-NHC ligand: synthesis, structure and reactivity

“…All these structural features suggest that the desired L − ligand has been obtained, featuring the dearomatized pyridine ring and an exocyclic C-C double bond, analogous to the related CNN pincer ligand 10 and picolyl-phosphine bidentate ligand. [16][17][18][19] The mesityl ring of one L − ligand in 4 is nearly parallel with the C 5 N ring of the other L − ligand (dihedral angles: 2.75 and 3.96°) with the shortest contact distance of ∼3.6 Å, suggesting weak π-π stacking interactions in between. (Fig.…”