871677-18-8Relevant academic research and scientific papers
Instability of square planar N3-ligand iridium(I) ethene complexes
Thewissen, Simone,Reijnders, Maike D. M.,Smits, Jan M. M.,De Bruin, Bas
, p. 5964 - 5972 (2005)
New, five-coordinate, iridium(I) bis-ethene complexes [fac-(bpa-R)Ir I(ethene)2]+ (1+: R = H, 2 +: R = Me, 3+: R = Bz; bpa-H = N,N-di(2-pyridylmethyl) amine, bpa-Me = N-methyl-N,N-di(2-pyridylmethyl)amine, bpa-Bz = N-benzyl-N,N-di(2-pyridylmethyl)amine) were prepared. In contrast to their previously reported rhodium analogues, these iridium species do not readily lose one of their two ethene fragments to form square planar mono-ethene complexes [mer-(bpa-R)IrI(ethene)]+. Heating complex 1+ results in N-H activation at the bpa-H ligand and formation of the dinuclear iridium(III) species [{(mer-μ2-bpa#)Ir III(ethyl)-(MeCN)}2]2+ (42+) with bridging amides (bpa# = bpa-H deprotonated at NHamine). Heating bpa-Bz complex 3+ results in aromatic C-H activation of the ligand benzyl group to form dinuclear iridium(III) species [{(bpa-Bz #)IrIII(μ2-H)}2]2+ (5 2+) with unsupported hydride bridges (bpa-Bz# = bpa-Bz cyclometalated at the benzylic C2-position). The dimeric structure of 5 2+ easily breaks up in MeCN, giving the mononuclear species [(bpa-Bz#)IrIII(H)(MeCN)]+ (6+). Complex 52+ is also light-sensitive: glass-filtered daylight converts it to a geometrical isomer, 72+, in which the cyclometalated benzyl functionality of one of the two ligands has switched its position with a pyridyl donor.
