Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131 Karlsruhe, Germany.
Dalton Trans. 2019 Nov 7;48(41):15397-15407. doi: 10.1039/c9dt02057h. Epub 2019 Jun 10.
The synthesis, characterisation and reactivity of new phosphine-functionalised tris(pyrazolyl)methane ligands (TpmPR, 2a-c, with R = Ph, nBu, iPr) are presented. The reaction of 2a-c with [Rh(CO)Cl] furnished N,P-heterochelate carbonyl complexes (3a-c), which were used to quantify the donor abilities of the ligands via IR spectroscopy. The coordination flexibility was demonstrated by treating representative members of this new ligand class with [CpRu(acn)][PF] (acn = acetonitrile), [(tht)AuCl] (tht = tetrahydrothiophene) and [Pd(allyl)Cl] providing either a N,N,P-heteroscorpionate complex (4) or the P-coordinated complexes (5,6) without any involvement of the pyrazolyl entities. With 2a and [Pd(cod)Cl], another P,N-heterochelate complex (7) was obtained, which served as a precursor for a heterobimetallic complex containing palladium and copper (8). Detailed NMR spectroscopic and X-ray crystallographic investigations have been performed on all new complexes.
本文介绍了新型膦功能化三（吡唑基）甲烷配体（TpmPR，2a-c，其中 R = Ph，nBu，iPr）的合成、表征和反应性。2a-c 与[Rh(CO)Cl]反应生成 N，P-杂环羰基配合物（3a-c），通过红外光谱法定量测定了配体的给电子能力。通过用[CpRu(acn)][PF]（acn = 乙腈）、[(tht)AuCl]（tht = 四氢噻吩）和[Pd(allyl)Cl]处理该新型配体类别的代表性成员，证明了配位的灵活性，得到了 N，N，P-杂冠醚配合物（4）或 P 配位配合物（5,6），而吡唑基实体没有任何参与。用 2a 和[Pd(cod)Cl]，得到了另一个 P，N-杂环配合物（7），它作为含有钯和铜的杂双金属配合物的前体（8）。对所有新配合物都进行了详细的 NMR 光谱和 X 射线晶体学研究。
