Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University of Erlangen-Nuremberg, Egerlandstrasse 1, Erlangen, Germany.
J Am Chem Soc. 2012 Sep 19;134(37):15538-44. doi: 10.1021/ja306647c. Epub 2012 Sep 6.
The synthesis and characterization of a series of manganese nitrides in a tripodal chelating tris(carbene) ligand framework is described. Photolysis of (TIMEN(xyl))Mn(N(3)) (where TIMEN(xyl) = tris[2-(3-xylylimidazol-2-ylidene)ethyl]amine) yields the isolable molecular Mn(IV) nitride, (TIMEN(xyl))Mn(N). Spectroscopic and DFT studies indicate that this Mn(IV) d(3) complex has a doublet electronic ground state. The metal-centered one-electron oxidation of this Mn(IV) species results in formation of the pentavalent Mn(V) nitride, (TIMEN(xyl))Mn(N). Unlike previously reported, tetragonal Mn(V) nitrides with a d(2), nonmagnetic S = 0 ground state, this trigonal bipyramidal complex has a triplet ground state S = 1. One-electron reduction of (TIMEN(xyl))Mn(N) produces the neutral, nonmagnetic trivalent [(TIMEN(xyl))Mn(N)] species with a d(4) low-spin, S = 0, ground state.
描述了一系列在三足螯合三（碳烯）配体骨架中的锰氮化物的合成和表征。(TIMEN(xyl))Mn(N(3))（其中 TIMEN(xyl)= 三[2-(3-二甲氧基苯基)咪唑-2-亚基]乙胺）的光解生成可分离的分子 Mn(IV)氮化物(TIMEN(xyl))Mn(N)。光谱和 DFT 研究表明，这种 Mn(IV)d(3)配合物具有双电子基态。该 Mn(IV)物种的中心金属单电子氧化导致形成五价 Mn(V)氮化物(TIMEN(xyl))Mn(N)。与之前报道的具有 d(2)、非磁性 S = 0 基态的四方 Mn(V)氮化物不同，这种三角双锥配合物具有三重态基态 S = 1。(TIMEN(xyl))Mn(N)的单电子还原生成中性、非磁性的三价[(TIMEN(xyl))Mn(N)]物种，具有 d(4)低自旋、S = 0 的基态。
