Corrigenda

Abstract

Structures (12)-( 14) and (21)-(23) are incorrect. The correct structures are shown below. NHBz w"' 0 0 X R 0 0 X (12) X=CO,H

1H NMR assignment corrections and 1H, 13C, 15N NMR coordination shifts structural correlations in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline

“…The 1 H NMR data for their salts were assigned in case of [Fe(bpy) 3 ]Cl 2 ,1 [Fe(bpy) 3 ](ClO 4 ) 2 ,2 [Fe(bpy) 3 ](PF 6 ) 2 ,3 [Ru(bpy) 3 ] Cl 2 ,4–7 [Ru(bpy) 3 ](SCN) 2 ,8 [Ru(bpy) 3 ](ClO 4 ) 2 ,2, 9 [Ru(bpy) 3 ] (PF 6 ) 2 ,10–18 [Ru(bpy) 3 ](BF 4 ) 2 ,19, 20 [Os(bpy) 3 ]Cl 2 ,5 [Os(bpy) 3 ] (ClO 4 ) 2 ,2, 21 [Os(bpy) 3 ](PF 6 ) 2 22 and [Fe(phen) 3 ](ClO 4 ) 2 ,23, 24 [Ru(phen) 3 ]Cl 2 ,7, 25–27 [Ru(phen) 3 ](ClO 4 ) 2 ,9, 14, 24, 28 [Ru(phen) 3 ] (PF 6 ) 2 ,29 [Ru(phen) 3 ](BF 4 ) 2 ,19 [Ru(phen) 3 ]SO 4 ,30 [Os(phen) 3 ] Cl 2 ,31 [Os(phen) 3 ](CF 3 SO 3 ) 2 32. It is really surprising, however, that their assignments were inconsistent, although the spectral patterns of such highly symmetric [M(LL) 3 ] 2+ cations were relatively simple, containing two doublets [H(3)/H(6)] and two triplets [H(4)/H(5)] for LL = bpy, or two doublets [H(2)/H(4)], a doublet of doublets [H(3)] and a singlet [H(5)] for LL = phen.…”

“…It is really surprising, however, that their assignments were inconsistent, although the spectral patterns of such highly symmetric [M(LL) 3 ] 2+ cations were relatively simple, containing two doublets [H(3)/H(6)] and two triplets [H(4)/H(5)] for LL = bpy, or two doublets [H(2)/H(4)], a doublet of doublets [H(3)] and a singlet [H(5)] for LL = phen. Particularly, the predominantly suggested orders of the 1 H resonances, H(3) > H(4) > H(5)/H(6) for [M(bpy) 3 ] 2+ 2, 3, 8–13, 15–17, 19–22 and H(4) > H(5) > H(2) > H(3) for [M(phen) 3 ] 2+ ,7, 9, 24, 26–28, 30, 31 contrasted to those proposed by some other authors: H(6) > H(3) > H(4) > H(5),1 H(6) > H(4) > H(3) > H(5),4 H(6) > H(5) > H(3) > H(4),5–7 H(3) > H(6) > H(5) > H(4)14 (all for [M(bpy) 3 ] 2+ ) and H(4) > H(2) > H(5) > H(3),29 H(2) > H(4) > H(3) > H(5),14 H(2) > H(3) > H(4) > H(5),19 H(2) > H(5) > H(4) > H(3),23, 32 H(2) > H(4) > H(5) > H(3)25 (all for [M(phen) 3 ] 2+ ). In our opinion, very large variations cannot be caused by the change of solvent and/or counterions, but they reflect erroneous attributions in some articles (the largest differences concerned peaks with the same multiplicity: H(3)/H(6) and H(4)/H(5) in bpy; H(2)/H(4) in phen).…”

Interspin Crossing and Reactivity

“…For example, pulsed UV photolysis of [Fe(CO) 5 ] leads to the formation of the unsaturated species [Fe(CO) x ] (x 2 ± 4), which show quite different reactivities in the recombination reaction with CO. [14,15] While the reactions of [Fe(CO) 2 ] and [Fe(CO) 3 ] with CO proceed at near gas kinetic rates, the reaction of [Fe(CO) 4 ] is about three orders of magnitude slower, with an activation energy of about 2.5 kcal mol À1 . [15] This unexpected behavior was explained by the spin change in the reaction since ground-state [Fe(CO) 4 ] is high spin (triplet [16] ), whereas ground-state [Fe(CO) 5 ] is low spin. Significant spin changes also occur in the sequential addition of CO to Mn to form [Mn(CO) 6 ] , and the CO exchange rates of the unsaturated fragments were discussed in terms of the requirements for spin conservation in ligand exchange reactions.…”

Spinumkehr und Reaktivität

“…drei Gröûenordnungen langsamer. [15] Dieser überraschende Unterschied wurde mit der Spinumkehr bei der Reaktion erklärt: [Fe(CO) 4 ] liegt im Grundzustand als High-spin-Komplex vor (Triplett [16] ), wohingegen [Fe(CO) 5 ] im Grundzustand ein Low-spin-Komplex ist. Bei der schrittweisen Addition von CO an Mn (3[Mn(CO) 6 ] ) kommt es ebenfalls zu ¾nderungen im Spinzustand; die gemessenen Geschwindigkeiten des CO-Austausches zwischen den ungesättigten Komplexfragmenten wurden dabei anhand der Spinerhaltung bei Ligandaustauschreaktionen interpretiert.…”