19394-85-5Relevant articles and documents
ReOCl3(PPh3)2] as a substrate for the synthesis of the rhenium(I) carbonyl complexes [Re(CO)2(OAc)(PPh 3)2] and [ReCl(CO)3(PPh3) 2
Krawczyk, Monika K.,Krawczyk, Marta S.,Siczek, Mi?osz,Lis, Tadeusz
, p. 60 - 62 (2013)
New preparative methods have been developed for the synthesis of the rhenium(I) carbonyl complexes [Re(CO)2(OAc)(PPh3) 2] (1) and [ReCl(CO)3(PPh3)2] (2). Acetic anhydride was decarbonylated during the course of its reaction with [ReOCl3(PPh3)2], resulting in the formation of the rhenium(I) carbonyl complex [Re(CO)2(OAc)(PPh3) 2] (1), which was subsequently converted almost quantitatively to [ReCl(CO)3(PPh3)2] (2) via the decarbonylation of its acetate group under acidic conditions.
Chemistry of coordinated nitroxyl. Reagent-specific protonations of trans-Re(CO)2(NO)(PR3)2 (R = Ph, Cy) that give the neutral nitroxyl complexes cis,trans-ReCl(CO)2(NH=O)(PR3)2 or the cationic hydride complex [trans,trans-ReH(CO)2(NO)(PPh3)2 +][SO3CF3-]
Southern,Green,Hillhouse,Guzei,Rheingold
, p. 6039 - 6046 (2008/10/08)
The reactions of hydrochloric and triflic acids with the five-coordinate nitrosyl complexes trans-Re(CO)2(NO)(PR3)2 (2a, R = Ph; 2b, R = Cy) have been investigated. Reaction of anhydrous HCl with 2 results in a formal protonation of the nitrosyl ligand and addition of chloride to the metal, giving the neutral nitroxyl complex cis,trans-ReCl(CO)2(NH=O)(PR3)2 (3a, R= Ph; 3b, R = Cy). Reaction of Bronsted bases with 3a or 3b results in clean conversion of 3 to 2 when the base is appropriately strong (pKb ? 7). Addition of HOSO2CF3 to solutions of 2a results in protonation at the metal and formation of the cationic rhenium hydride [trans,trans-ReH(CO)2(NO)(PPh3)2 +][SO3CF3-] (4) in 74% yield; the deuteride [trans, trans-Re(2H)(CO)2(NO)(Pph3)2 +][SO3CF3-] (4-d) was analogously prepared from 2HOSO2CF3. 4 crystallized from CH2Cl2/Et2O solution in the orthorhombic space group Pnma, with a = 17.2201(2) A, b = 23.6119(3) A, c = 9.2380(2) A, and Z = 4. The least-squares refinement converged to R(F) = 0.039 and R(wF2) = 0.063 for the 4330 unique data with I > 2σ(I). The structure of 4 shows that the hydride (Re - H = 1.74 A) occupies the position trans to the linear nitrosyl ligand (Re - N - O = 178.1(4)°) in the pseudooctahedral complex cation. Complex 4 does not react with chloride to give 3a. DFT calculations carried out on free nitroxyl and its model complexes [Re(CO)5(NH=O)+] (5), [mer, trans-Re(CO)3(NH=O)(PH3)2+] (6), and cis,trans-ReCl(CO)2(NH=O)(PH3)2 (7) indicate that coordinated nitroxyl acts as both a σ-donor and π-acceptor ligand, consistent with the observed trend for ν(NO) in free HN=O (1563 cm-1), [mer,trans-Re(CO)3(NH=O)(PPh3)2+] (1, 1391 cm-1), 3a (1376 cm-1), and 3b (1335 cm-1).
Electronic Emission and Absorption Spectroscopy of the Rhenium Complexes Re(CO)3Cl(Phosphine)2
Ramsis, M. N.
, p. 849 - 856 (2007/10/02)
The compounds Re(CO)3Cl(L)2, L = triphenylphosphine, tri-p-tolyphosphine, and Re(CO)3Cl(L'), L' = 1,2-bis(diethylphosphinoethane) are luminescent in solution and in crystalline form when excited between 351 nm and 514 nm at temperatures ranging from 10 K to room temperature.The absorption spectra contain a weak (E ca. 10 M-1 cm-1) band in the visible region of the spectrum between 400 and 500 nm.The lowest energy transition giving rise to these spectroscopic features is assigned to a d-d transition. - Keywords.Rhenium complexes; Electronic emission; Absorption.
