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

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 oxidati ve 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 re act 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 exces s 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 Els evier Science B.V. All rights reserved.