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

Research output: Contribution to journalArticle (Academic Journal)peer-review

18 Citations (Scopus)
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9-Amino-9-phosphabicyclo[3.3.1]nonanes, (PhobPNHR'; R = Me or (i)Pr) 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([double bond, length as m-dash]NMeH)PPhob]Cl is formed which, upon addition of [PtCl2(NC(t)Bu)2] gives the zwitterionic complex [PtCl3(PhobP([double bond, length as m-dash]NMeH)PPhob)]. The neutral PhobP([double bond, length as m-dash]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)2294-307
Number of pages14
JournalDalton Transactions
Issue number5
Early online date11 Jan 2016
Publication statusPublished - 7 Feb 2016

Structured keywords

  • BCS and TECS CDTs


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