Pseudohalogeno-Metallverbindungen. LXXV. Pentacarbonylrhenium-und Triphenylphosphangold-Komplexe mit Pseudohalogeniden: (OC)5ReX,Ph3PAuX (X = ONC(CN)2, o-MeC6H4SO2C(CN)2,o-MeC6H4SO2NCN,Ph2(S)PNCN)

Pseudohalogeno Metal Compounds. LXXV. Pentacarbonylrhenium and Triphenylphosphinegold Complexes of Pseudohalide Anions: (OC)₅ReX, Ph₃PAuX (x = ONC(CN)₂, o-MeC₆H₄SO₂C(CN)₂, o-MeC₆H₄SO₂NCN, Ph₂(S)PNCN) The pseudohalides (X^?) nitrosodicyanmethanide, o-tosyldicyanmethanide, o-tosylcyanamide and diphenylthiophosphinylcyanamide react with the Organometallic Lewis Acids (OC)₅Re⁺ (as (OC)₅ReFBF₃) and Ph₃PAu⁺ (as Ph₃PAuNO₃) to give the neutral title complexes (OC)₅Re—X and Ph₃PAu? X, respectively. X-ray diffraction shows that nitroso-dicyanmethanide is coordinated through the nitroso N-atom to the Re(CO)₅ fragment. Cyanide-N-coordination is observed for the complexes with o-tosyldicyanmethanide and o-tosylcyanamide whereas diphenylthiophosphinylcyanamide is S-coordinated to the gold atom. Spectroscopic data (IR, NMR) of 1–6 are described.     

A Study of the Nitroso Spin Adducts of the Pentacarbonyl Rhenium Radical

Nitrosobenzene (NB) and nitroso-tetr-butane (NtB) were used to trap the photogenerated rhenium pentacarbonyl radical. Self trapped radicals and spin adducts were studied in detail by EPR spectroscopy. In methylene chloride, both nitroxide and anilino spin adducts can be observed with NtB at ?30°. In contrast, only the nitroxide spin adduct of nitrosobenzene was observed in either hexane, or methylene chloride solution. This solvent controlled spin adduct chemistry, can be explained in terms of the solute-solvent interaction.     

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

The addition of Re(CO)₅⁺ [as Re(CO)₅FBF₃] to P(CN)₃ and to P(CN)₂^– affords the complexes [Re(CO)₅]₃P(CN)₃(BF₄)₃ and Re(CO)₅P(CN)₂, respectively. The spectroscopic data indicate that Re(CO)₅⁺ is coordinated to each of the three cyano groups of P(CN)₃ to give {P[C≡N‐Re(CO)₅]₃}[BF₄]₃, whereas the pseudohalide P(CN)₂^– is bonded to the rhenium cation through the phosphorus atom.