Complexation associated rearrangement of iminobiphosphines to diphosphinoamines

The reaction of the iminobiphosphines RN[dbnd]>PPh<sub>2</sub>-PPh<sub>2</sub>, where R = C<sub>6</sub>H<sub>4</sub>(p-CN), C<sub>6</sub>H<sub>4</sub>(m-CN), C<sub>6</sub>H<sub>4</sub>(o-C<sub>6</sub>H<sub>5</sub>), C<sub>6</sub>F<sub>5</sub> or C<sub>6</sub>H<sub>4</sub>(o-CF<sub>3</sub>), with one mol. equiv. of M(cod)Cl<sub>2</sub> (M = Pd or Pt) results in a rearrangement of the N[dbnd]>P[sbnd]>P unit to the more commonly encountered P-N-P unit, forming mono-chelating complexes of general formula M{RN(PPh<sub>2</sub>)<sub>2</sub>}Cl<sub>2</sub>. The related reaction of the same range of iminobiphosphines with Pt(cod)Cl<sub>2</sub> (but not Pd(cod)Cl<sub>2</sub>) in 2:1 ratio affords complexes of general formula [Pt{RN(PPh<sub>2</sub>)<sub>2</sub>}<sub>2</sub>]<sub>2</sub>Cl. All 15 complexes are isolated in moderate to high yield and they have been fully characterised by spectroscopic methods. Six complexes, viz. [M{C<sub>6</sub>H<sub>4</sub>(p-CN)N(PPh<sub>2</sub>)<sub>2</sub>}Cl<sub>2</sub>], [M{C<sub>6</sub>H<sub>4</sub>(m-CN)N(PPh<sub>2</sub>)<sub>2</sub>}Cl<sub>2</sub>] and [M{C<sub>6</sub>H<sub>4</sub>(o-C<sub>6</sub>H<sub>5</sub>)N(PPh<sub>2</sub>)<sub>2</sub>}Cl<sub>2</sub>] (M = Pd and Pt), have been characterised in the solid state by single crystal X-ray diffraction anal.


Published in:
INORGANICA CHIMICA ACTA, 359, 9, 2635-2643
Year:
2006
Laboratories:


Note: The status of this file is: EPFL only


 Record created 2006-05-30, last modified 2018-03-17

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