Metalation and Transmetalation Studies on Ph2PN(iPr)P(Ph)N(iPr)H for Selective Ethene Trimerization to 1-Hexene

• Published in: Organometallics 2010-11, Vol.29 (21), p.5263-5268
• Main Authors: Peitz, Stephan, Peulecke, Normen, Aluri, Bhaskar R, Müller, Bernd H, Spannenberg, Anke, Rosenthal, Uwe, Al-Hazmi, Mohammed H, Mosa, Fuad M, Wöhl, Anina, Müller, Wolfgang
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om100371f

Different organometallic compounds of the new aminodiphosphinoamine ligand Ph2PN(iPr)P(Ph)N(iPr)-H (1) are reported that are relevant model complexes for the selective ethene trimerization system consisting of ligand 1, CrCl3(THF)3, and Et3Al that produces 1-hexene in more than 90% yield and high purity. The lithiation of 1 by n-BuLi in the presence of tetramethylethylenediamine (tmeda) yields the mononuclear compound Ph2PN(iPr)P(Ph)N(iPr)-][Li(tmeda)] (2). Without using tmeda the dinuclear species [Ph2N(iPr)P(Ph)N(iPr)-Li]2 (3) was obtained. By addition of a Grignard reagent to the ligand solution the bis(aminodiphosphinoamide)magnesium complex [Ph2PN(iPr)P(Ph)N(iPr)-]2Mg (4) could be isolated. Reaction of Li[CpCrCl3] with 3 leads to the formation of the model compound CpCrCl[-N(iPr)P(Ph)N(iPr)PPh2] (5), which can be alkylated with Na[Et4Al] to form the corresponding ethyl compound CpCrEt[-N(iPr)P(Ph)N(iPr)PPh2] (7). In THF the formation of EtCrCl2(THF)3 (8) directly from the reaction of CrCl3[Ph2PN(iPr)P(Ph)N(iPr)-H](THF) (6) with Et3Al could be observed. The organometallic chemistry of 1 gives hints on possible species and activation mechanisms in the catalysis, which have to be considered for a better understanding of the catalytic system.