Reactivity Differences of Pt0 Phosphine Complexes in C-C Bond Activation of Asymmetric Acetylenes

Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt(PhC CR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butylphosphino)ethane (dtbpe), and 1-diisopropylphosphino-2-dimethylaminoethine (dippdmae) chelates. (dippe)Pt(eta(2)-PhC CCH3) (1a), (dippe)Pt(eta(2)-PhC CCF3) (1b), and (dippe)Pt(eta(2)-PhC CC(CH3)(3)) (1c) showed no thermal reactivity at 160 degrees C, but 1b showed evidence for C-C cleavage to form (dippe)Pt(Ph)(C CCF3) upon irradiation with UV light (>300 nm). In comparison, dtbpe analogues of these metal complexes, (dtbpe)Pt(eta(2)-PhC CCH3) (2a), (dtbpe)pt(eta(2)-phC CCF3) (2b), and (dtbpe)Pt(eta(2)-PhC CC(CH3)(3)) (2c), showed either C-H or C-C activation products upon photolysis. 2b produced (dtbpe)Pt(Ph)(C CCF3), but 2a or 2c showed the formation of (dtbpe)Pt(D)(C6D5) (2D) by activation of the C6D6 solvent. Compounds 2a-c showed no thermal reactivity at 160 degrees C. Two complexes with the hemilabile chelate dippdmae were synthesized and fully characterized, (dippdmae)Pt(eta(2)-PhC CCF3) (3b) and (dippdmae)Pt(eta(2)-PhC CC(CH3)(3)) (3c). C-C cleavage products of the type (L-2)Pt(Ph)(C CCF3) were observed only upon photolysis of compounds 1b, 2b, and 3b.