Organometallic Lewis Acids, Part LIX^[1] Pentacarbonylrhenium Complexes with Phosphorus Tricyanide and Di­cyanophosphide

Abstract

The addition of Re(CO) 5 + [as Re(CO) 5 FBF 3 ] to P(CN) 3 and to P(CN) 2 affords the complexes [Re(CO) 5 ] 3 P(CN) 3 (BF 4 ) 3 and Re(CO) 5 P(CN) 2 , respectively. The spectroscopic data indicate that

Synthesis of Heavy Dicyanamide Homologues from Air‐Stable Precursors

“…There is precedent for such differences in the few characterized DCP‐metal complexes that have been reported . For example, though (DCA)Re(CO) 5 features coordination from the DCA nitrile groups, the homologous DCP complex likely binds to rhenium through the central atom, as evidenced by the significant deshielding of the 31 P NMR chemical shift relative to [Na([18]crown‐6)][DCP] …”

“…[53] For example,t hough (DCA)Re(CO) 5 features coordination from the DCA nitrile groups, [54] the homologous DCP complexl ikely binds to rheniumt hrough the central atom, as evidenced by the significant deshielding of the 31 PNMR chemical shift relative to [Na( [18]crown-6)][DCP]. [55] In conclusion, am ore safe and efficient synthetic protocol for the generationo fd icyanophosphidea nionsb yP + transfer from at riphosphenium salt, [dppeP][BPh 4 ]i sr eported. We have also prepared the remarkably stable As + transfer salt [dppeAs][BPh 4 ], which is not hindered by reactive anions or si-multaneousP + transfer,a nd used it to isolatet he dicyanoarsenide anion for the first time.…”

Organometallic Lewis Acids LX. Pentacarbonylrhenium Complexes [(OC)5Re-L]+BF4-with N-Donor-Ligands L = Tetrazole, Dimetylaminopyridine (DMAP), Triphenyliminophosphoranes and with Triphenylphosphine Oxide

“…In continuation of our studies we report in the following examples on the reactivity of the pentacarbonylrheniumtetrafluorborate (OC) 5 ReFBF 3 , which occurs by facile substitution of the BF 4 ligand under very mild conditions and with high yields , …”

Template Synthesis of NPN′ Pincer-type Ligands at Titanium Using an Ambiphilic Phosphide Scaffold

“… − However, although the difference between phosphides and phospheniums seems obvious, the electronic properties of substituents X can somewhat blur the distinction between these two classes of compounds . Thus, phosphide D and phosphenium E (which, respectively, contain electron-withdrawing and electron-donating substituents) both display ambiphilic character. − In extreme cases, net charges become all but insignificant: compound F can bind up to two metal centers, − which clearly makes it a competent Lewis base …”