| Abstract
| - The complexReIII(benzil)(PPh3)Cl3(2) is used to synthesize a variety of ReIII andReII polypyridyl complexes ofthe typecis-[ReIII(L2)2Cl2]+,[ReII(L2)3]2+,ReIII(L3)Cl3,[ReIII(L3)2Cl]2+,and[ReIII(L4)Cl2]+,where L2 = bpy (3and 6), tbpy (4 and 7), phen(5 and 8); L3 = terpy (9and 10); L4 = TMPA (11).The complexcis-[ReIII(bpy)2Cl2]+ (3) is a useful synthon inthe formation of complexes of the type[Re(bpy)2Lx]n+that are six- or seven-coordinate ReIII complexes (13, 16,and 18) or octahedral ReII or ReIcomplexes (12 and 17). The[ReIII(terpy)2Cl]2+(10) complex can be reduced to form the ReIcomplex, [ReI(terpy)2]+(21) and then electrochemically reoxidizedto form new complexes of the type[ReIII(terpy)2L]n+.Similar behavior is observed for the[ReII(bpy)3]2+(6)complex where[ReIII(bpy)3(tBuNC)]3+(20) and[ReI(bpy)3]+(19) may be formed. The electrochemistry ofthesecomplexes is discussed in relation to their reactivity and the observedπ-acidity of the polypyridyl ligands. Inaddition, X-ray crystal structures forcis-[ReIII(bpy)2Cl2]PF6(3) and[ReI(bpy)3]PF6(19) are reported. cis-[ReIII(bpy)2Cl2]PF6(3,ReC20H16N4Cl2F6P)crystallizes in the monoclinic space group C2/cwith Z = 4 and latticeparameters a = 15.043(5) Å, b =13.261(4) Å, c = 12.440(4) Å, and β =108.86(2)° at −100 °C.[ReI(bpy)3]PF6 (19,ReC30H24N6F6P)crystallizes in the rhombohedral space groupR3̄c(h) (No. 167) withZ = 12 and latticeparameters a = 13.793(3) Å and c =51.44(3) Å at −100 °C.
- The complexReIII(benzil)(PPh3)Cl3is used to synthesize a variety of low-valent polypyridyl rheniumcomplexes of typescis-[ReIII(L2)2X2]+,ReIII(L3)Cl3,[ReIII(L3)2Cl]2+,[ReIII(L4)Cl2]+,[ReII(L2)3]2+,and[ReI(L2)3]+,where L2 = bpy, phen; L3 = terpy; andL4 = tris(2-pyridylmethyl)amine. An ORTEPof [Re(bpy)3]+ isshown.
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