de Krom Iris, Lutz Martin, Müller Christian
Schuit Institute of Catalysis, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.
Dalton Trans. 2015 Jun 14;44(22):10304-14. doi: 10.1039/c5dt01261a.
Replacing nitrogen by phosphorus in otherwise similar structures changes the properties of the resulting compounds significantly due to the electronic differences that exist between these heteroatoms. While the "hard" nitrogen atom of the pyridine moiety acts as a good σ-donor, the "soft" phosphorus atom of the phosphinine core results in a rather strong π-acceptor capacity. A series of novel group 6 complexes [M(CO)4(L^L)] (M = Cr(0), Mo(0), W(0)) have been synthesized, in which L^L is either 2-(2'-pyridyl)-4,6-diphenylphosphinine (P,N) or the corresponding bipyridine derivative, 2-(2'-pyridyl)-4,6-diphenylpyridine (N,N) as a chelating, bidentate ligand. The here presented results describe a detailed investigation of the structural and spectroscopic properties of the coordination compounds [M(CO)4(P,N)] and [M(CO)4(N,N)] (M = Cr(0), Mo(0), W(0)), leading to a better understanding of such intriguing aromatic phosphorus heterocycles.
在其他方面相似的结构中用磷取代氮，会因这些杂原子之间存在的电子差异而显著改变所得化合物的性质。吡啶部分的“硬”氮原子是良好的σ供体，而磷杂苯核心的“软”磷原子则具有相当强的π受体能力。已合成了一系列新型的6族配合物[M(CO)₄(L^L)]（M = Cr(0)、Mo(0)、W(0)），其中L^L为2-(2'-吡啶基)-4,6-二苯基磷杂苯（P,N）或相应的联吡啶衍生物2-(2'-吡啶基)-4,6-二苯基吡啶（N,N）作为螯合双齿配体。本文给出的结果描述了对配位化合物[M(CO)₄(P,N)]和[M(CO)₄(N,N)]（M = Cr(0)、Mo(0)、W(0)）的结构和光谱性质的详细研究，从而更好地理解这类有趣的芳族磷杂环。
