[Mn(CO)m(CN t Bu)n(L)p(LL)] ClO 4类型的几种羰基锰配合物(m + n + p = 4; m = 1-3; n = 1-3 3;p= 0,1; L = P(OMe)3,CNPh ; L = L =2,2′-联吡啶(bipy),1,10-菲咯啉(phen),双(叔丁基)-1,从fac- [Mn(CO)3(CN t Bu)开始制备4-重氮杂2,3-二烯(t Bu-DAB),N,N,N',N'-四甲基乙二胺(tmed)) (LL)] ClO 4或fac- [Mn(CO)3 {P-(OMe)3 }(LL)] ClO 4,并使用ONMe 3作为脱羰剂。根据可能的中间体的性质讨论了取代反应产物的立体化学。
[(CO)3(dppe)Mn(OH2)]BF4 (1). A synthetically versatile compound and its use as a probe for determining the preferred site of coordination on ambident ligands
作者:Padmanabha R. Ettireddy、Milton Orchin
DOI:10.1016/j.poly.2005.08.032
日期:2006.3
Previous work in this laboratory has shown that the Mn(I) octahedral complex, [(CO)(3)(dppe)Mn(OH2)]BF4 (1), may be used for the synthesis of many related complexes by the ready replacement of the aqua ligand by neutral and anionic ligands, leading to new complexes having a variety of functional groups sigma (eta(1)) bonded to the Mn atom. This procedure has now been extended to ligands possessing phenolic and carboxylic acid groups, including amino acids. Compound 1 is used as a probe to compare the relative coordinating ability of different heteroatoms on ambident ligands. The H-1 NMR spectra of the resulting complexes show two signals at room temperature for the four protons (each 2H m) of the dppe-Mn metallacyle whose position depends on the specific atom of the ligand that is attached to the metal. The spectrum of 1, however, shows only one signal (4H m). On cooling to -53 degrees C this signal is split in two (both 2H, in) owing to a slowing of the rapid reversible dissociation of the aqua ligand. (c) 2005 Elsevier Ltd. All rights reserved.