146684-40-4Relevant articles and documents
Synthesis of Cationic Half-sandwich Rhodium(I) Complexes of 1,4,7-Trithiacyclononane (aneS3). The Single-crystal Structures of aneS3)(C2H4)2>PF6, aneS3)(C8H12)>BF4 and aneS3)(C6H4)>PF6*0.25OEt2
Blake, Alexander J.,Gould, Robert O.,Halcrow, Malcolm A.,Schroeder, Martin
, p. 2197 - 2208 (1994)
Reaction of hepta-2,5-diene)> with 2 molar equivalents of 1,4,7-trithiacyclononanone(aneS3) in the presence of NaBF4 or NH4PF6 at 293 K, or treatment of or with 1 molar equivalent of aneS3 and NH4PF6 afforded aneS3)L(L')>X in moderate yields.The crystal structure of the complex aneS3)(C2H4)2>PF6 has been determined: monoclinic, space group P21/n, a = 11.487(3), b= 9.459(3), c = 15.745(6) Angstroem, β = 105.54(3) deg and Z = 4.The cation adopts a trigonal-bipyramidal geometry, with one equatorial and one axial ethene ligand.The complex aneS3)(cod)>BF4 crystallises in the triclinic space group P with a = 11.491(13), b = 12.803(6), c = 13.377(15), α = 88.12(7), β = 70.30(8), γ = 74.68(7) deg and Z = 4.The two molecules in each asymmetric unit also adopt distorted trigonal-bipyramidal stereochemistries, with the conformation in molecule 1 being related to that of molecule 2 by a 6 deg rotation of the macrocyclic ring about the central M-aneS3 axis.The complex aneS3)(C4H6)>PF6 crystallises in the monoclinic space group C2/c with a = 18.612(6), b = 8.679(5), c = 23.756(5), β = 96.844(18) deg and Z = 8.The structure shows a quasi-square-pyramidal complex cation.Treatment of with aneS3 and NH4PF6 yielded the dimeric complex aneS3)2(μ-CO)3>2.Reaction of aneS3)(C2H4)L>(+) with halogenated substrates afforded insoluble aneS3)X3> (X = Cl or I), while no reaction was observed with C6H6 or SiEt3H.Spectroscopic, structural and chemical evidence indicates that the aneS3)>(+) fragment has a high electrophilic character.
