P=C-N Systems: Potential of benzazaphospholes for transition metal complexes with non-classical P hybrid ligands, for bulky P-substituted heterocyclic phosphane ligands, complexes and catalysts and for benzazaphospholium salts as precursors of P,N-heteroc

芳香族稳定的P=C-N杂环，特别是各种N-和C-取代的1，3-苯并膦及其相关的共面四环P=C-N-杂环的反应性研究应以下列目标为目标：-单齿和双齿杂环P=C-N-配体和(P=C-N)，P-或(P=C-N)，N杂化配体与单价和二价过渡金属离子作为可能用于过渡金属催化的新型配合物的合成和结构表征。-开发一种新的合成策略，以合成单齿和双齿大而富电子的P-叔丁基取代P，N杂环膦配体在P=C-N结构基团上的控制加成，重点是不对称N-取代基诱导的对映选择性P=C加成。这将导致新的不对称P，N配体，这可能有助于过渡金属催化的对映体选择性有机转化。-苯并膦转化为N，P-二戊基苯并磷酸盐，探索它们的性质和合成潜力，以获得新的P，N-杂环卡宾配合物。通过对这类化合物的分离和结构表征，我们希望了解五元环中两个杂原子的固定对这些卡宾性质的影响。到目前为止，只有非循环代表是已知的。各种类型的卡宾络合物在催化反应中有着极其广泛的应用。

Reactivity studies of aromatically stabilized P=C-N heterocycles, specially of various N- and C-substituted 1,3-benzazaphospholes and related coplanar tetracyclic P=C-N-heterocycles, shall be carried out with the following objectives:- Synthesis and structural characterization of complexes of mono- and bidentate heterocyclic P=C-N-ligands and (P=C-N),P- or (P=C-N),N hybrid ligands with mono- and divalent transition metal ions as novel type of complexes for potential use in transition metal catalysis.- Development of a new synthesis strategy to mono- and bidentate bulky and electronrich P-tert-butyl substituted P,N heterocyclic phosphane ligands by controlled addition at the P=C-N structure group with emphasis to enantioselective P=C addition, induced by an asymmetric N-substituent. This shall lead to new asymmetric P,N ligands which might be useful for transition metal catalyzed enantioselective organic transformations. - Conversion of benzazaphospholes into N,P-dineopentyl-benzazaphospholium salts, exploration of their properties and synthesis potential for the access to novel P,N-heterocyclic carbene complexes. By isolation and structural characterization of such a complex we want to gain knowledge on the influence of the fixation of the two heteroatoms in a five-memebred ring on the properties of these carbenes. So far only acyclic representatives are known. Carbene complexes of various types have found extremely manifold applications in catalytic reactions.