An experimental and DFT computational study of a novel zerovalent tetracarbonyl tungsten complex of 2-(2′-pyridyl)quinoxaline

Synthesis and characterization of the new complex W(CO)(4)(2,2'-pq), (1), where 2,2'-pq = 2-(2'-pyridyl)quinoxaline, is presented. The non-symmetric ligand 2,2'-pq belongs to the general class of quinoxalines, which are natural products yielding rich coordination chemistry. Complex (1) crystallizes in space group P2(1/n) with alpha = 9.601(6) angstrom, b = 16.735(1) angstrom, c = 10.315(8) angstrom, Z = 4 and V = 1616.0(19) angstrom(3). Although its structure resembles those of W(CO)(4)(phen) and W(CO)(4)(bpy), some distortions that stem from 2,2'-pq's asymmetry are present. DFT calculations reveal a ground state consisting of HOMO, HOMO - 1 and HOMO - 2, mainly of metal and carbonyl character, while LUMO is diimine oriented. The bonding scheme of (1) is illustrated after its consideration as been consisted by two fragments, namely W(CO)4 and 2,2'-pq, acting as a donor and acceptor of electron density, respectively. In that scheme, back-bonding interaction of the main core to 2,2'-pq is mainly related to the mixing of HOMO - 2 from W(CO)(4) moiety with LUMO from 2,2'-pq moiety. The performed TDDFT calculations, not only in the gas phase but also combined with the conductor like polarizable continuum model (CPCM), reveal that the lowest in energy highly solvatochromic transition of (1) can be ascribed as a HOMO - 2 LUMO transition and it is better described as MLCT/LLCT, underlying the CO diimine contribution. The solvatochromic behaviour of (1) is anticipated by DFT/CPCM calculations and is probed in detail by absorption and NMR spectroscopy. The correlation of the lowest-energy-band maximum to the dipole moment of the corresponding solvents provides overall good linear fits, while the correlation to the dielectric constant affords good linear patterns only after the segregation of the solvents into groups. The H-1 NMR data of 2,2-pq and (1) reveal an increase of the solvent influence to the chemical shifts of the diimine ligand after its coordination to the metal and suggest two different types of solvent-effects for the complex and the ligand, respectively. The observed proton shifts of (1) are related with the results of the Mulliken population analysis in solvents of different polarity; the transition from CCl4 to MeOH seems to signify a charge transfer from the axial COs and the central metal to the equatorial COs and the internal nuclei of 2,2'-pq. (c) 2005 Elsevier B.V. All rights reserved.