89656-69-9Relevant academic research and scientific papers
New synthetic routes to biscarbonylbipyridinerhenium(I) complexes cis, trans-[Re(X2bpy)(CO)2(PR3)(Y)](n+) (X2bpy = 4,4'-X2-2,2'-bipyridine) via photochemical ligand substitution reactions, and their photophysical and electrochemical properties
Koike, Kazuhide,Tanabe, Junji,Toyama, Shigeki,Tsubaki, Hideaki,Sakamoto, Kazuhiko,Westwell, Jeremy R.,Johnson, Frank P. A.,Hori, Hisao,Saitoh, Hideki,Ishitani, Osamu
, p. 2777 - 2783 (2008/10/08)
Photochemical ligand substitution of fac-[Re(X2bpy)(CO)3(PR3)]+ (X2bpy = 4,4'-X2-2,2'-bipyridine; X = Me, H, CF3; R = OEt, Ph) with acetonitrile quantitatively gave a new class of biscarbonyl complexes, cis,trans-[Re(X2bpy)(CO)2(PR3)(MeCN)]+, coordinated with four different kinds of ligands. Similarly, other biscarbonylrhenium complexes, cis,trans-[Re(X2bpy)(CO)2(PR3)(Y)](n+) (n = 0, Y = Cl-; n = 1, Y = pyridine, PR'3), were synthesized in good yields via photochemical ligand substitution reactions. The structure of cis,trans-[Re(Me2-bpy)(CO)2{P(OEt)3}(PPh3)](PF6) was determined by X-ray analysis. Crystal data: C38H42N2O5F6P3Re, monoclinic, P21/a, a = 11.592(1) A, b = 30.953(4) A, c = 11.799(2) A, V = 4221.6(1) A3, Z = 4, 7813 reflections, R = 0.066. The biscarbonyl complexes with two phosphorus ligands were strongly emissive from their 3MLCT state with lifetimes of 20-640 ns in fluid solutions at room temperature. Only weak or no emission was observed in the cases Y = Cl-, MeCN, and pyridine. Electrochemical reduction of the biscarbonyl complexes with Y = Cl- and pyridine in MeCN resulted in efficient ligand substitution to give the solvento complexes cis,trans-[Re(X2bpy)(CO)2(PR3)(MeCN)]+.
Synthetic routes to luminescent 2,2′-bipyridyl complexes of rhenium: Preparation and spectral and redox properties of mono(bipyridyl) complexes of rhenium (III) and rhenium(I)
Caspar, Jonathan V.,Sullivan, B. Patrick,Meyer, Thomas J.
, p. 2104 - 2109 (2008/10/08)
New methods of preparing 2,2′-bipyridyl (bpy) complexes of rhenium are described. The procedures involve starting complexes of Re(IV), Re(III), and Re(I) and result in new bpy complexes of the type fac-ReIII(bpy)(P)Cl3, trans,cis-[ReIII(bpy)(P)2Cl2]+, and trans,cis-[Re(bpy)(P)2(CO)2]+, where P is a tertiary phosphine. In addition, the complex cis-[Re(bpy)2(CO)2]+ has been prepared, which is a rare example of a bis(bipyridyl)rhenium species. Aspects of the NMR spectra, electronic spectra, and electrochemistry of the complexes are discussed, and special attention is given to the fact that the ReI(bpy) complexes luminescence in fluid solution at room temperature. They represent a growing class of potentially exploitable metal-to-ligand charge-transfer (MLCT) excited-state species of Re(I) that have potential interest for use in photochemical energy conversion schemes.
