Revisiting the Synthesis and Elucidating the Structure of Potassium Cyclopentadienyldicarbonylruthenate, K[CpRu(CO)2]

Year:

2014

Type of Publication:

Artikel

Autoren:

Kalz, Kai F.; Kindermann, Nicole; Xiang, Sheng-Qi; Kronz, Andreas; Lange, Adam; Meyer, Franc

Journal:

Organometallics

Volume:

33

Nummer:

6

Seiten:

1475-1479

BibTex:

@article{doi:10.1021/om500107j, author = "Kai F. Kalz and Nicole Kindermann and Sheng-Qi Xiang and Andreas Kronz and Adam Lange and Franc Meyer", abstract = " Known procedures for the synthesis of K[CpRu(CO)2] (KRp) via reductive cleavage of the ruthenium dimer Rp2 were found to be inconsistent and have thus been revisited, and a revised protocol using K[HB(sec-Bu)3] (K-Selectride) as the reducing agent is now reported that gives yellow KRp in crystalline form in around 40\% yield. The structure of KRp·THF has been determined by X-ray diffraction, representing the first crystallographic characterization of an Rp– salt. Inevitably the reductive cleavage of Rp2 also gives a poorly soluble black solid as an additional product, which has now been analyzed by a variety of methods, including 13C MAS NMR spectroscopy using 13CO-labeled material. The black solid has been identified as a polymeric Cp/Ru/CO compound with both bridging and terminal CO ligands in a 3:1 ratio. The present report may stimulate the use of the [CpRu(CO)2]− (Rp–) anion, which has been barely exploited as yet in comparison to its popular congener [CpFe(CO)2]− (Fp–). ", doi = "10.1021/om500107j", journal = "Organometallics", number = "6", pages = "1475-1479", title = "{R}evisiting the {S}ynthesis and {E}lucidating the {S}tructure of {P}otassium {C}yclopentadienyldicarbonylruthenate, {K}[{C}p{R}u({CO})2]", url = " http://dx.doi.org/10.1021/om500107j ", volume = "33", year = "2014", }

Kurzzusammenfassung:

Known procedures for the synthesis of K[CpRu(CO)2] (KRp) via reductive cleavage of the ruthenium dimer Rp2 were found to be inconsistent and have thus been revisited, and a revised protocol using K[HB(sec-Bu)3] (K-Selectride) as the reducing agent is now reported that gives yellow KRp in crystalline form in around 40\% yield. The structure of KRp·THF has been determined by X-ray diffraction, representing the first crystallographic characterization of an Rp– salt. Inevitably the reductive cleavage of Rp2 also gives a poorly soluble black solid as an additional product, which has now been analyzed by a variety of methods, including 13C MAS NMR spectroscopy using 13CO-labeled material. The black solid has been identified as a polymeric Cp/Ru/CO compound with both bridging and terminal CO ligands in a 3:1 ratio. The present report may stimulate the use of the [CpRu(CO)2]− (Rp–) anion, which has been barely exploited as yet in comparison to its popular congener [CpFe(CO)2]− (Fp–).