Oxidative addition reactions of Rh(SbPh3)(3)(CO)X (X = Cl, Br) with organic phenyl-substituted propargyl compounds. Rhodium(III) phenylpropargyl products and their conversion to rhodiacyclic complexes


Kayan A. , Wojcicki A.

INORGANICA CHIMICA ACTA, cilt.319, ss.187-193, 2001 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 319
  • Basım Tarihi: 2001
  • Doi Numarası: 10.1016/s0020-1693(01)00457-1
  • Dergi Adı: INORGANICA CHIMICA ACTA
  • Sayfa Sayısı: ss.187-193

Özet

Reactions of Rh(SbPh3)(3)(CO)X (X = Cl (1), Br (2)) with PhC=CCH2Y (Y = OTs, Cl, Br) in CH2Cl2 at ambient temperature lead to formation of the oxidative addition products Rh(SbPh3)(2)(CO)X(Y)(eta'-CH2C=CPh) (X = Cl, Y = OTs (3), Cl (4), Br (5); X = Br, Y = OTs (6), Br (7)). Complexes 3 and 6 each react with pyridine at room temperature to afford the rhodiacyclopent-3-ene-2-ones Rh(SbPh3)(2)(py)X(eta (2)-C(O)C(Ph)=C(OTs)CH2) (X = Cl (8), Br (9)). Treatment with AgOTs converts 8 to Rh(SbPh3)(2)(py)(OTs)(eta (2)-C(O)C(Ph)=C(OTs)CH2) (10). Addition of AgOTf (or AgBF4) and then immediately an excess of PhC=CCH2Br to a CH2Cl2 solution of 1 at ambient temperature affords an orange solid that is formulated tentatively as [Rh(SbPh3)(2)(CO)Cl(eta (3)-CH2CCPh)]OTf (or -BF4) (11a and 11b). All new complexes were characterized by a combination of elemental analysis, FAB mass spectrometry, IR and NMR (H-1 and C-13{H-1}) spectroscopy and conductance measurements. (C) 2001 Elsevier Science B.V. All rights reserved.