Six-coordinate 16-electron d4 complexes of group (VI), particularly tungsten, have been found to assume configurations that span from the fully octahedral to the fully trigonal prismatic, with some exhibiting different degrees of distortion between the two geometries. Six-coordinate d4 complexes of tungsten are quite rare in the literature and are also highly reactive due to tungsten's propensity to form 7-coordinate complexes, which would allow for a more stable 18-electron configuration. Here we report the synthesis of six-coordinate 16-electron d4 complexes of type [W(S-S)(CO)2(L)x] (S-S: bdt2-=benzene-1,2-dithiolate; mnt2-= maleonitrile-2,3-ditholate, Lx=1: phen=1,10-phenanthroline; bpm*=bis(3,5-dimethyl-1-pyrazolyl)methane; enH2Et2=N,N-diethylethylenediamine, Lx=2: py=pyridine). Also, we present a more accesible route to the known complex [W(tdt-2)(CO)2(phen)] (tdt2-=toluene-3,4-dithiolate) and a reworking of the synthesis of 18-electron 7-coordinate complexes of type [WI2(CO)3(L)x] (Lx=1=phen, bpm*,Lx=2=py). All complexes have been characterized spectroscopically and electrochemically as well as having their geometries and electronic structures scrutinized by employing Density Functional Theory (DFT).

Six-coordinate 16-electron complexes of tungsten (II): Synthesis, electrochemistry, and density functional theory

249th National Meeting (2015)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.