An experimental and theoretical study of the coordination and donor properties of tris-2-pyridyl-phosphine ligands

Abstract

The donor properties of a range of multidentate 2-pyridyl-phosphines were evaluated using different experimental and computational methods.

Exploring Phosphine Electronic Effects on Molybdenum Complexes: A Combined Photoelectron Spectroscopy and Energy Decomposition Analysis Study

“…The phosphorus(III) ligands were chosen because they belong to one of the most used ligand family in catalytic processes [38][39][40][41] and several experimental and/or theoretical works have already been devoted to the study of their electronic influence on metals. 37,[42][43][44][45][46][47]…”

“…Our objective was to determine to which extent this experimental method may be correlated to theoretical data. The phosphorus­(III) ligands were chosen because they belong to one of the most used ligands family in catalytic processes, − and several experimental and/or theoretical works have already been devoted to the study of their electronic influence on metals. ,− …”

Facile synthesis of a nickel(0) phosphine complex at ambient temperature

“…Using the related ligand P(6-Me-2-py) 3 or the more closely related ligands (Me 2 N) 2 P(2-py) and (MeO)P(2-py) 2 in place of phosphine 1 does not result in the corresponding Ni(0) complexes, suggesting that characteristics like the Lewis acidity and the -donor/-acceptor character are key to the reactivity of 1. 28 The importance of the Lewis acidity of the P centre in particular can be related to the proposed mechanism involved, and it is noteworthy that being the most Lewis acidic phosphine we have explored fluorination of the P-atom of 1 would produce the most stable intermediate (A, Scheme 3). Scheme 2.…”

Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

“…competition between phosphorus and nitrogen coordination. [122] This is reminiscent of the selectivity problems in the generation of cationic phosphines by alkylation of a phosphorus substituent (see Chapter 1.3.2.1, Scheme 27). However, in this regard, the ligand of Holm 172 provides more controlled conditions due to higher denticity (Scheme 50).…”

“…The two Cu(I) centers in complex 244 reveal a pentacoordinate environment where the soft Cu + is not only coordinated by two 2,2′-bipyridin-6-yl moieties but also additionally to a phosphorus of another Cu + complex. [122] The resulting dimeric structure exhibits two Cu(I) centers in a distorted tetragonal pyramidal configuration (τ5 = 0.3670/0.3353 [145] ). The nearly centrosymmetric arrangement is symmetry-broken by the different orientations of the two dangling 2,2′-bipyridin-6-yl moieties and the different tetragonal pyramidal distortion of the two Cu + centers.…”