Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 30, 48149 Münster, Germany.
J Am Chem Soc. 2012 Sep 19;134(37):15443-56. doi: 10.1021/ja305406x. Epub 2012 Sep 10.
A unique hexaphosphane featuring a 2,2'-bi(1,2,3-triphosphacyclopentane) moiety (19) and an ethylene-bridged bis-isotetraphosphane (27(c,m)) were both selectively prepared in efficient one-pot syntheses from easily accessible tris(3,5-dimethyl-1-pyrazolyl)phosphane (14) and 1,2-bis(phenylphosphanyl)ethane (18(c,m)). The formation of 27(c,m) is an example of a highly efficient P-P bond formation via protolysis. In contrast, the formation of 19 comprises P-N/P-P bond metathesis steps. This constitutes a novel synthetic approach toward the preparation of complex polyphosphanes. Detailed spectroscopic investigations form the basis for a mechanistic understanding of this unprecedented methodology. Furthermore, the preparation of a unique dinuclear iron-carbonyl complex which features hexaphosphane 19 as a bridging ligand illustrates the potential use of complex polyphosphanes such as 19 as ligands in transition metal chemistry.
一种独特的六磷烷，具有 2,2'-双（1,2,3-三磷杂环戊烷）部分（19）和乙烯桥联的双异四磷烷（27(c,m)），均通过从易于获得的三（3,5-二甲基-1-吡唑基）膦（14）和 1,2-双（苯膦基）乙烷（18(c,m)）进行高效一锅合成法选择性制备。27(c,m)的形成是通过质子化进行高效 P-P 键形成的实例。相比之下，19 的形成包括 P-N/P-P 键交换步骤。这构成了制备复杂多磷烷的新合成方法。详细的光谱研究为这种前所未有的方法的机理理解奠定了基础。此外，独特的双核铁羰基配合物的制备，其特征是六磷烷 19 作为桥连配体，说明了复杂多磷烷如 19 作为过渡金属化学中配体的潜在用途。
