scholarly journals Substituent effects in phosphine ligands

2011 ◽  
Vol 30 (1) ◽  
Author(s):  
C. Alicia Renison ◽  
D. Bradley G. Williams ◽  
Alfred J. Muller
Keyword(s):  
Nmr Spectroscopy ◽  
High Resolution ◽  
Molecular Modelling ◽  
31P Nmr ◽  
Substituent Effects ◽  
Phosphine Ligands ◽  
31P Nmr Spectroscopy ◽  
Electronic Effects ◽  
X Ray ◽  
X Ray Crystallography

The study illustrates the use of the P-atom to evaluate steric and electronic effects in P-containing organic compounds. The work involves the synthesis of substituted triarylphosphines and their corresponding Rh Vaska complexes. High resolution X-ray crystallography, molecular modelling, 31P NMR spectroscopy and IR will be used to quantify substituent effects.

Synthesis, Characterization, and Crystal Structures of [Cu(ca2en)(PPh3)(X)] (X = Cl, Br, I, NCS, N3) Complexes

2003 ◽  
Vol 56 (4) ◽  
pp. 323 ◽  
Author(s):  
Guido Kickelbick ◽  
Mehdi Amirnasr ◽  
Aliakbar D. Khalaji ◽  
Saeed Dehghanpour
Keyword(s):  
Infrared Spectroscopy ◽  
Nmr Spectroscopy ◽  
31P Nmr ◽  
Mixed Ligand ◽  
Bond Breaking ◽  
31P Nmr Spectroscopy ◽  
Distorted Tetrahedron ◽  
Nmr Studies ◽  
X Ray ◽  
Elemental Analyses

Novel mixed-ligand copper(I) complexes, [Cu(ca2en)(PPh3)X] (ca2en = N,N′-bis(trans-cinnamaldehyde)-1,2-diaminoethane, X = Cl (1), Br (2), I (3), NCS (4), N3 (5)), have been synthesized and characterized by 1H and 31P NMR spectroscopy, infrared spectroscopy, and elemental analyses. The single crystal X-ray structures of complexes (1)–(5) have been determined. All five complexes reveal discrete monomeric structures in the crystal. The geometry around the copper atom is in each case a distorted tetrahedron, with the distortion most pronounced in (3). The NCS− and N3− are coordinated as terminal ligands and the NCS− ligand is N-bonded in (4). Dynamic 31P NMR studies show partial bond breaking in solution.

Substituenteneinflüsse auf Synthese und Eigenschaften von Hexakis[phosphanaurio(I)]methanium(2+)bis(tetrafluoroboraten) / Substituent Effects in Synthesis and Properties of Hexakis[phosphineaurio(I)]methanium(2 +) Bis(tetrafluoroborates)

1992 ◽  
Vol 47 (12) ◽  
pp. 1725-1735 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Benno Brachthäuser ◽  
Siegfried Gamper ◽  
Annette Schier ◽  
Oliver Steigelmann
Keyword(s):  
Nmr Spectra ◽  
Room Temperature ◽  
Substituent Effects ◽  
Reaction Times ◽  
Phosphine Ligands ◽  
Electronic Effects ◽  
X Ray ◽  
Magnetic Resonance Parameters ◽  
Interstitial Carbon Atom ◽  
C Nmr

Polyaurated carbon complexes of the type [(L–Au)6C]2+ with functionalized phosphine ligands have been prepared by the reaction of the phosphinegold(I) chlorides R(Ph)2PAuCl (R = p-C6H4-Cl 2a,p-C6H4-Br 2b,p-C6H4-CH3 2c,p-C6H4-OCH3 2d,p-C6H4-COOH 2e, p-C6H4–N(CH3)2 2f), R2(Ph)PAuCl (R = p-C6H4-N(CH3)2 2g) and R3PAuCl (R = p-C6H4-N(CH3)2 2h) with tetrakis(dimethoxyboryl)methane in HMPT at room temperature. Clearly depending on the different inductive and mesomeric effects, the preparation of the clusters with substituents like –CH3 3c, –OCH3 3d and –N(CH3)2 3f needs shorter reaction times and the products show better solubility in organic solvents than those with functional groups like –Cl 3a, –Br 3b and –COOH 3e. The 31P magnetic resonance parameters are correlated with electronic effects of the substituents, but the chemical shift of the interstitial carbon atom in the 13C-NMR spectra is largely independent of the coordinating ligands. For the phosphinegold(I) chlorides 2f–h X-ray structure analyses have been performed.

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