摘要：

Reaction of [Rh2L2L′2Cl2]{L,L′= C2H4, cod or nbd; L = C2H4, L′= PPri3 or P(C6H11)3; cod = cycloocta-1,5-diene, nbd = norbornadiene (bicyclo[2.2.1]hepta-2,5-diene)} with 2 molar equivalents of 1,4,7-trithiacyclononane([9]aneS3) in the presence of NaBF4 or NH4PF6 at 293 K, or treatment of [Rh(C4H6)2Cl] or [Rh(CO)Cl(PPh3)2] with 1 molar equivalent of [9]aneS3 and NH4PF6 afforded [Rh([9]aneS3)L(L′)]X [L,L′= C2H4, cod, nbd or C4H6; L = C2H4, L′= PPri3, P(C6H11)3; L = CO, L′= PPh3; X = BF4 or PF6] in moderate yields. The crystal structure of the complex [Rh([9]aneS3)(C2H4)2]PF6 has been determined: monoclinic, space group P21/n, a= 11.487(3), b= 9.459(3), c= 15.745(6), β= 105.54(3)° and Z= 4. The cation adopts a trigonal-bipyramidal geometry, with one equatorial and one axial ethene ligand. The complex [Rh([9]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)° 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° rotation of the macrocyclic ring about the central M–[9]aneS3 axis. The complex [Rh([9]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)° and Z= 8. The structure shows a quasi-square-pyramidal complex cation. Treatment of [Rh2(CO)4Cl2] with [9]aneS3 and NH4PF6 yielded the dimeric complex [Rh2([9]aneS3)2(-CO)3][PF6]2. Reaction of [Rh([9]aneS3)(C2H4)L]+[L = C2H4 or P(C6H11)3] with halogenated substrates afforded insoluble [Rh([9]aneS3)X3](X = Cl or I), while no reaction was observed with C6H6 or SiEt3H. Spectroscopic, structural and chemical evidence indicates that the [Rh([9]aneS3)]+ fragment has a high electrophilic character.

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