Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Inorg Chem. 2009 Mar 16;48(6):2507-17. doi: 10.1021/ic801855y.
The tetradentate tris(phosphino)silyl ligand [SiP(iPr)(3)] ([SiP(iPr)(3)] = Si(o-C(6)H(4)P(i)Pr(2))(3)) has been prepared, and its complexation with iron, cobalt, nickel, and iridium precursors has been explored. Several coordination complexes have been thoroughly characterized and are described. These include, for example, the divalent trigonal bipyramidal metal chlorides [SiP(iPr)(3)]M-Cl (M = Fe, Co, Ni), as well as the monovalent dinitrogen adducts [SiP(iPr)(3)]M-N(2) (M = Fe, Co, Ir), which are compared with related [SiP(Ph)(3)]M-Cl and [SiP(Ph)(3)]M-N(2) species (M = Fe, Co). Complexes of this type represent the first examples of terminal dinitrogen adducts of monovalent iron, and the ligand architecture allows examination of a unique class of dinitrogen adducts with a trans-disposed silyl donor. Oxidation of the appropriate [SiP(R)(3)]M-N(2) precursors affords the divalent iron triflate [SiP(Ph)(3)]Fe(OTf) and trivalent cobalt triflate {[SiP(iPr)(3)]Co(OTf)}{OTf} complexes, which are of interest for group transfer studies because of the presence of a labile triflate ligand. Comparative electrochemical, structural, and spectroscopic data are provided for these complexes.
四齿三（膦）硅基配体SiP(iPr)(3)] = Si(o-C(6)H(4)P(i)Pr(2))(3))已被制备，并对其与铁、钴、镍和铱前体的络合进行了探索。几种配合物已被彻底表征并进行了描述。例如，二价三角双锥金属氯化物[SiP(iPr)(3)]M-Cl（M = Fe、Co、Ni），以及单价二氮配位物[SiP(iPr)(3)]M-N(2)（M = Fe、Co、Ir），它们与相关的[SiP(Ph)(3)]M-Cl 和[SiP(Ph)(3)]M-N(2)物种（M = Fe、Co）进行了比较。这类配合物代表了单价铁的末端二氮加合物的第一个实例，配体结构允许对具有反式排布的硅供体的独特的二氮加合物类进行考察。适当的[SiP(R)(3)]M-N(2)前体的氧化得到二价铁三氟甲磺酸酯[SiP(Ph)(3)]Fe(OTf)和三价钴三氟甲磺酸酯{[SiP(iPr)(3)]Co(OTf)}{OTf}配合物，由于存在易位的三氟甲磺酸酯配体，这些配合物对基团转移研究很有意义。提供了这些配合物的电化学、结构和光谱比较数据。
