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• W1965451570 abstract "A trifluoromethyl iridium(I) complex Ir(CF3)(CO)2(PPh3)2 (1 has been prepared by the reaction of Hg(CF3)2 with IrH(CO)2(PPh3)2, or by thermal decomposition of Ir(COCF3)(CO)2(PPh3)2 (3), which is produced from (CF3CO)2O and a reduced iridium(−I) species. Either the reaction of IrH(CO)(PPh3)3 with Hg(CF3)2 or the reversible thermal decarbonylation of 1 yields the coordinatively unsaturated complex Ir(CF3)(CO)(PPh3)2 (2). Derivatives Ir(CF3)L(CO)(PPh3)2 (L = C2F4 (4), L = C2H4 (5), L = O2 (6)) result from treatment of 1 with tetrafluoroethylene, or 2 with ethylene or oxygen, respectively. Both 1 and 2 undergo oxidative addition of Cl2, I2, HCl, H2 and CH3I to give trifluoromethyl iridium(III) complexes IrCl2(CF3)(CO)(PPh3)2 (7), IrI2 (CF3)(CO)(PPh3)2 (8), IrHCl(CF3)(CO)(PPh3)2 (9), cis-IrH2(CF3)(CO)(PPh3)2 (10) and IrI(CH3)(CF3)(CO)(PPh3)2 (11), respectively. The iodo ligand in 11 is labile and can be replaced by an acetonitrile ligand to yield [Ir(CH3)(CF3)(L)(CO)(PPh3)2]ClO4 (L = CH3CN (12)). This ligand can in turn be replaced by p-tolylisocyanide (L = CN-p-C6H4CH3 (13)) or Cl− to give IrCl(CH3)(CF3)(CO)(PPh3)2 (14). Complexes 1 and 9 each react with AlCl3 to give the difluoromethyl species IrCl2(CF2H)(CO)(PPh3)2 (15). A difluorocarbene iridium(I) complex, IrCl(CF2)(CO)(PPh3)2 (16), has been prepared by thermal decarbonylation of Ir(COCF2Cl)(CO)2(PPh3)2 (18), and a complex containing both CF3 and CF2 ligands, Ir(CF2)(CF3)(CO)(PPh3)2 (17), has been made by treatment of either IrCl(CO)(PPh3)2, 2 or 16 with Cd(CF3)2 · glyme. Both 16 and 17 are hydrolysed to give carbonyl species IrCl(CO)2(PPh3)2 and 1, respectively, while 16 reacts with t-butylamine to give an isocyanide complex, IrCl(CN-t-C4H9)(CO)(PPh3)2 (20). Addition of HCl to 16 or 17 produces 15 or 9, respectively. Complexes 4, 11 and 17 have been characterised by X-ray diffraction studies." @default.
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• W1965451570 date "1990-08-01" @default.
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• W1965451570 title "Trifluoromethyl, difluorocarbene and tetrafluoroethylene complexes of iridium and the crystal structures of IrI(CH3)(CF3)(CO)(PPh3)2, Ir(CF3)(C2F4)(CO)(PPh3)2 and Ir(CF3)(CF2)(CO)(PPh3)2" @default.
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• W1965451570 doi "https://doi.org/10.1016/0022-328x(90)87258-f" @default.
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