Aminophobanes: Hydrolytic stability, tautomerism and application in Cr-catalysed ethene oligomerisation

Mairi F. Haddow, Judit Jaltai, Martin Hanton, Paul G. Pringle*, Laura E. Rush, Hazel A. Sparkes, Christopher H. Woodall

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

9-Amino-9-phosphabicyclo[3.3.1]nonanes, (PhobPNHR′; R = Me or iPr) are readily prepared by aminolysis of PhobPCl and are significantly less susceptible to hydrolysis than the acyclic analogues Cy2PNHR′. Treatment of Cy2PNHMe with Cy2PCl readily gave Cy2PNMePCy2. By contrast, treatment of PhobPCl with PhobPNHMe in the presence of Et3N does not afford PhobPNMePPhob but instead the salt [PhobP(NMeH)PPhob]Cl is formed which, upon addition of [PtCl2(NCtBu)2] gives the zwitterionic complex [PtCl3(PhobP(NMeH)PPhob)]. The neutral PhobP(NMe)PPhob is accessible from PhobNMeLi and is converted to the chelate [PdCl2(PhobPNMePPhob)] by addition of [PdCl2(cod)]. The anomalous preference of the PhobP group for the formation of PPN products is discussed. The unsymmetrical diphos ligands PhobPNMePAr2 (Ar = Ph, o-Tol) are prepared, converted to [Cr(CO)4(PhobPNMePAr2)] and shown to form Cr-catalysts for ethene oligomerisation, producing a pattern of higher alkenes that corresponds to a Schulz-Flory distribution overlaid on selective tri/tetramerisation.

Original languageEnglish
Pages (from-to)2294-2307
Number of pages14
JournalDalton Transactions
Volume45
Issue number5
Early online date11 Jan 2016
DOIs
Publication statusE-pub ahead of print - 11 Jan 2016

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