Reduction of the two trivalent 2,6-[2,6-(i-Pr)2C6H5]N=C(CH3)2(C5H3N)VCl3 and [2,6-[2,6-(i-Pr)2C6H3]N-C=(CH2)2(C5H3N)]VCl(THF) complexes with excess NaH afforded two corresponding end-on dinitrogen-bridged complexes [2,6-[2,6-(i-Pr)2C6H5]N=C(CH3)2(C5H3N)V]2(m-N2).(hexane) (1) and [[2,6-[2,6-(i-Pr)2C6H3]N-C=(CH2)2(C5H3N)]V]2(m-N2).(hexane) (3). Despite their very close structural similarity, the two species have completely different natures. The first is paramagnetic and may be regarded as generated by the two-electron attack of two formally zerovalent vanadium moieties on the same N2 unit. In the nearly diamagnetic 3 instead, the N2 unit has been reduced by two vanadium atoms, formally divalent. Structural analysis and DFT calculations have indicated that partial reduction of the bridging nitrogen occurred for both complexes while, in the case of 1, substantial metal-to-ligand electron transfer also occurs.
Dinitrogen partial reduction by formally zero- and divalent vanadium complexes supported by the bis-iminopyridine system / Vidyaratne, Indu; Gambarotta, Sandro; Korobkov, Ilia; Budzelaar, Petrus Henricus Maria. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 44:5(2005), pp. 1187-9-1189. [10.1021/ic048358+]
Dinitrogen partial reduction by formally zero- and divalent vanadium complexes supported by the bis-iminopyridine system
BUDZELAAR, Petrus Henricus Maria
2005
Abstract
Reduction of the two trivalent 2,6-[2,6-(i-Pr)2C6H5]N=C(CH3)2(C5H3N)VCl3 and [2,6-[2,6-(i-Pr)2C6H3]N-C=(CH2)2(C5H3N)]VCl(THF) complexes with excess NaH afforded two corresponding end-on dinitrogen-bridged complexes [2,6-[2,6-(i-Pr)2C6H5]N=C(CH3)2(C5H3N)V]2(m-N2).(hexane) (1) and [[2,6-[2,6-(i-Pr)2C6H3]N-C=(CH2)2(C5H3N)]V]2(m-N2).(hexane) (3). Despite their very close structural similarity, the two species have completely different natures. The first is paramagnetic and may be regarded as generated by the two-electron attack of two formally zerovalent vanadium moieties on the same N2 unit. In the nearly diamagnetic 3 instead, the N2 unit has been reduced by two vanadium atoms, formally divalent. Structural analysis and DFT calculations have indicated that partial reduction of the bridging nitrogen occurred for both complexes while, in the case of 1, substantial metal-to-ligand electron transfer also occurs.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.