Polydentate phosphines

Abstract

a b s t r a c tPhosphines are one of the most important classes of ligands in chemistry, in both the industrial and academic spheres. This review deals with the design and properties of polydentate phosphines, an original and broad class of multidentate ligands. The multidentate nature of these species has led to special properties, in which the spatial proximity of phosphorus atoms is crucial. The first part gives an overview of oligodentates polyphosphines in which is discussed the types and the basic routes for their synthesis. The review continues with the most important synthetic routes for obtaining complexes. Because of huge amount of literature data this review is not exhaustive, but it collects the most relevant findings in this area. The restriction to structural and spectroscopic properties allows us for a well organized handling of the complex material.

New Superhindered Polydentate Polyphosphine Ligands P(CH2CH2PtBu2)3, PhP(CH2CH2PtBu2)2, P(CH2CH2CH2PtBu2)3, and their Ruthenium(II) Chloride Complexes

“…RuCl 2 (P 3 P 3 tBu ) (6). While, RuCl 2 (P 3 P 3 tBu ) (6) could be prepared in a similar manner to the syntheses of RuCl 2 (P 2 P 3 tBu ) (4) and RuCl 2 (PhP 2 P 2 tBu ) (5) (by the direct reaction of RuCl 2 (PPh 3 ) 3 with P 3 P 3 tBu ligand), the separation of RuCl 2 (P 3 P 3 tBu ) (6) from the triphenylphosphine byproduct was difficult.…”

“…The cloudy suspension was stirred for 1 h, then the solid was isolated by filtration to give dichloro(bis(2-di(tertbutyl)phosphinoethyl)phenylphosphine-κ 3 P)ruthenium(II) (0.255 g, 0.407 mmol, 37%) as a yellow solid. 6 MHz, dichloromethane-d 2 ): δ 137.7 (d, 1 J C−P = 36.3 Hz, C Ar ); 132.4 (d, J C−P = 8.7 Hz, C Ar ); 130.4 (d, J C−P = 2.4 Hz, C Ar ); 128.8 (d, J C−P = 9.3 Hz, C Ar ); 40.7 (d, 1 J C−P = 17.9 Hz, PC(CH 3 ) 3 ); 36.9 (d, 1 J C−P = 11.4 Hz, PC(CH 3 ) 3 ); 31.9 (dd, J C−P = 31.0 Hz, J C−P = 6.3 Hz, CH 2 ); 31.8 (d, 2 J C−P = 2.9 Hz, PC(CH 3 ) 3 ); 29.2 (s, PC(CH 3 ) 3 ); 25.3 (dd, J C−P = 22.7 Hz, J C−P = 13 Hz, CH 2 ).…”

New Heteroleptic RuII/Diphosphine Complexes with Cytotoxicity against Human Breast and Murine Ascitic Sarcoma 180 Tumor Cells

“…46 Theoretical results support these experimental data, in which the replacement of the two chlorido atoms by the picolinate anion stabilizes the complexes. As it is well known, oxidation potential can be related to ionization potential (Eº α E i ) 49,50 since both refer to the withdraw of electrons, which in turn can be associated to the highest occupied molecular orbital (HOMO) energy (E i α −E HOMO ). 51 Therefore, oxidation potential can be related to the HOMO energy, 52 i.e., the lower the HOMO energy, the higher the oxidation potential.…”

Diphosphanylmetallocenes of Main‐Group Elements

“…Phosphines are one of the most important classes of ligands in coordination chemistry throughout the periodic table, owing to their strong σ‐donor abilities [1] . Within this class, bidentate ligands in the form of bis(phosphanyl) compounds are widely recognized for their strong binding capabilities owing to the chelate effect [2a] . Modification of the linker between the phosphanyl groups in these bis(phosphines) can have a strong effect on the bite angle, which is of great importance with regards to steric and electronic properties, and thus for applications in coordination chemistry and catalysis [2b,c] .…”