Comparing spectroscopic and electrochemical properties of complexes of type Cp'M(eta(3)-C3H5)(CO)(2) (Cp' = Cp, Ind, Flu): A complementary experimental and DFT study

authors	Goncalves, IS; Veiros, LF; Gamelas, CA; Cabrita, C; Calhorda, MJ; Geraldes, CFGC; Green, J; Packham, E; Drew, MGB; Felix, V; Santos, AG; Romao, CC
nationality	International
journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
author keywords	Molybdenum; Allyl complexes; Mo-95 NMR; DFT calculations; PES spectroscopy
keywords	MOLECULAR-ORBITAL METHODS; EXTENDED BASIS-SETS; VALENCE BASIS-SETS; ORGANOMETALLIC CONFORMATIONAL EQUILIBRIA; BRIDGED HETEROBIMETALLIC COMPLEXES; DENSITY-FUNCTIONAL CALCULATIONS; RAY PHOTOELECTRON-SPECTROSCOPY; CONTINUUM SOLVATION MODELS; EFFECTIVE CORE POTENTIALS; TRANSITION-METAL ATOMS
abstract	A series of allyl complexes of the general formula [Cp'Mo(eta(3)-C3H5)(CO)(2)], where Cp' = Cp, CpMe, Cp*, Ind, IndMe, IndMe2, Flu, and three tungsten analogues, has been prepared and characterized by H-1, C-13, and Mo-95 NMR, cyclic voltammetry, and the structure of [IndMo(eta(3)-C3H5)(CO)(2)] was determined by Xray single crystal analysis. Two conformers, corresponding to the two extreme orientations of the allyl ligand (endo and exo), have been identified in solution by H-1 and Mo-95 NMR for all the complexes, except for [FluMo(eta(3)-C3F15)(CO)(2)], which only presents an exo conformation in solution. A Mo-95 NMR investigation also shows the influence of electron donor capability of the Cp' ligands on the Mo-95 chemical shifts of the Mo center. He I and He II photoelectron spectra probe the electron richness of the metal center and the electronic structure of the complexes. Cyclic voltammetry studies show one oxidation process, which is only reversible for the Cp derivatives. DFT calculations provided a reliable way to determine ionization energies, and reflected very well the trends of the other properties, from the Mo-95 NMR chemical shifts, to vibration frequencies, and oxidation potentials. (1) 2015 Elsevier BY. All rights reserved.
publisher	ELSEVIER SCIENCE SA
issn	0022-328X
year published	2015
volume	792
beginning page	154
ending page	166
digital object identifier (doi)	10.1016/j.jorganchem.2015.04.001
web of science category	Chemistry, Inorganic & Nuclear; Chemistry, Organic
subject category	Chemistry
unique article identifier	WOS:000359201500023