Coordination chemistry of new selective ethylene trimerisation ligand Ph2PN(iPr)P(Ph)NH(R) (R = iPr, Et) and tests in catalysis

Bhaskar Reddy Aluri; Normen Peulecke; Stephan Peitz; Anke Spannenberg; Bernd H. Müller; Stefan Schulz; Hans-Joachim Drexler; Detlef Heller; Mohammed H. Al-Hazmi; Fuad M. Mosa; Anina Wöhl; Wolfgang Müller; Uwe Rosenthal

doi:10.1039/C0DT00440E

Coordination chemistry of new selective ethylene trimerisation ligand Ph₂PN(ⁱPr)P(Ph)NH(R) (R = ⁱPr, Et) and tests in catalysis†‡

Bhaskar Reddy Aluri,^a Normen Peulecke,^a Stephan Peitz,^a Anke Spannenberg,^a Bernd H. Müller,^a Stefan Schulz,^a Hans-Joachim Drexler,^a Detlef Heller,^a Mohammed H. Al-Hazmi,^b Fuad M. Mosa,^b Anina Wöhl,^c Wolfgang Müller^c and Uwe Rosenthal*^a

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* Corresponding authors

^a Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Straße 29a, Rostock, Germany
E-mail: uwe.rosenthal@catalysis.de

^b Saudi Basic Industries Corporation, P.O. Box 42503, Riyadh, Saudi Arabia

^c Linde AG, Linde Engineering Division, Dr -Carl-von-Linde-Straße 6-14, Pullach, Germany

Abstract

The synthesis of [Ph₂PN(ⁱPr)P(Ph)NH(R)] (R = ⁱPr, Et) (1, 2) is described and the structure of 2 has been determined by single-crystal X-ray analysis. Compound 1 readily reacts with chromium(0), nickel(0), nickel(II), palladium(II), platinum(II) and iron(II) complexes to give four-membered rings (3–10) via P,P′ coordination. The molecular structures of [Cr(CO)₄{Ph₂PN(ⁱPr)P(Ph)NH(R)-P,P′}] (R = ⁱPr, Et) (3, 4), [Cr(CO)₃(NCCH₃){Ph₂PN(ⁱPr)P(Ph)NH(ⁱPr)-P,P′}] (5), [Ni{Ph₂PN(ⁱPr)P(Ph)NH(ⁱPr)-P,P′}₂] (6), cis-[MX₂{Ph₂PN(ⁱPr)P(Ph)NH(ⁱPr)-P,P′}] (M = Ni, Pd, Pt; X = Cl or Br) (7, 8, 9) and trans-[Fe(NCCH₃)₂{Ph₂PN(ⁱPr)P(Ph)NH(ⁱPr)-P,P′}₂](BF₄)₂ (10) have been determined by X-ray diffraction. In the solid state, these complexes show tight phosphine bite angles in the range 67.89(2)° to 74.97(4)° and the central nitrogen atom adopts an almost planar (sp²) geometry. Complexes 3, 5, 6, 7 and 10 are tested for their catalytic activity in ethylene oligomerisation. Additionally, complex 10 is tested in hydrogenation of olefins.

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Coordination chemistry of new selective ethylene trimerisation ligand Ph₂PN(ⁱPr)P(Ph)NH(R) (R = ⁱPr, Et) and tests in catalysis†‡

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Coordination chemistry of new selective ethylene trimerisation ligand Ph₂PN(ⁱPr)P(Ph)NH(R) (R = ⁱPr, Et) and tests in catalysis

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