Synthesis of β-P,N Aminophosphines and Coordination Chemistry to Pd<sup>II</sup>. X-ray Structures
of [PdCl<sub>2</sub>(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>,κ<i>N</i>)] and [PdCl(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>)]
Jacques Andrieu
Jean-Michel Camus
Jochen Dietz
Philippe Richard
Rinaldo Poli
10.1021/ic000867y.s001
https://acs.figshare.com/articles/dataset/Synthesis_of_-P_N_Aminophosphines_and_Coordination_Chemistry_to_Pd_sup_II_sup_X-ray_Structures_of_PdCl_sub_2_sub_Ph_sub_2_sub_PCH_sub_2_sub_CH_Ph_NHPh-_i_P_i_i_N_i_and_PdCl_sup_3_sup_-C_sub_3_sub_H_sub_5_sub_Ph_sub_2_sub_PCH_sub_2_sub_CH_Ph_NHPh-_i_P_i_/3600735
The reaction of the CN bond in PhCHNPh with the carbanionic species Ph<sub>2</sub>PCH<sub>2</sub><sup>-</sup>, leading to the <i>N</i>-phenyl
β-aminophosphine Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh, <b>L</b><b><sup>1</sup></b><sup></sup>, is described. This molecule reacts with different organic electrophiles
to afford related compounds Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NPhX (X = SiMe<sub>3</sub>, <b>L</b><b><sup>2</sup></b><sup></sup>; COPh, <b>L</b><b><sup>4</sup></b><sup></sup>), [Ph<sub>2</sub>MePCH<sub>2</sub>CH(Ph)NHPh]<sup>+</sup>(I<sup>-</sup>),
<b>L</b><b><sup>3</sup></b><sup></sup>, and [Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)N(Ph)CO]<sub>2</sub>, <b>L</b><b><sup>5</sup></b><sup></sup>, containing two amido and two phosphino functions. The coordination
properties of <b>L</b><b><sup>1</sup></b><sup></sup>, <b>L</b><b><sup>2</sup></b><sup></sup>, and <b>L</b><b><sup>4</sup></b><sup></sup> have been studied in palladium chemistry. The X-ray structure of [PdCl<sub>2</sub>(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>,κ<i>N</i>)] shows the bidentate coordination mode for the <b>L</b><b><sup>1</sup></b><sup></sup> ligand with equatorial C<sub>Ph</sub>−N<sub>Ph</sub> phenyl
groups. [PdCl<sub>2</sub>(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>,κ<i>N</i>)] crystallizes at 298 K in the space group <i>P</i>2<sub>1</sub>/<i>n</i> with cell parameters
<i>a</i> = 10.689(2) Å, <i>b</i> = 21.345(3) Å, <i>c</i> = 12.282(2) Å, β = 90.294(12)°, <i>Z</i> = 4, <i>D</i><sub>calcd</sub> = 1.526. The reaction
between 2 equiv of <b>L</b><b><sup>1</sup></b><sup></sup> and [PdCl(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)]<sub>2</sub> affords the [PdCl(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>)] complex in
which an unexpected N−H···Cl intramolecular interaction has been observed by an X-ray diffraction analysis.
[PdCl(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(Ph<sub>2</sub>PCH<sub>2</sub>CH(Ph)NHPh-κ<i>P</i>)] crystallizes at 298 K in the monoclinic space group <i>Cc</i> with cell
parameters <i>a</i> = 10.912(1) Å, <i>b</i> = 17.194(2) Å, <i>c</i> = 14.169(2) Å, β = 100.651(9)°, <i>Z</i> = 4, <i>D</i><sub>calcd</sub> = 1.435. Neutral
and cationic alkyl or allyl palladium chloride complexes containing <b>L</b><b><sup>1</sup></b><sup></sup> are also reported as well as a neutral allyl
palladium chloride complex containing <b>L</b><b><sup>4</sup></b><sup></sup>. Variable-temperature <sup>31</sup>P{<sup>1</sup>H} NMR studies on the allyl complexes
show that the η<sup>3</sup>/η<sup>1</sup> allyl interconversion is enhanced by a positive charge and also by a N−H···Cl intramolecular
interaction.
2001-03-01 00:00:00
cell parameters
allyl palladium chloride complexes
allyl palladium chloride
carbanionic species Ph 2 PCH 2
L 4
L 2
L 1
L 1 ligand
bidentate coordination mode
allyl complexes show
space group Cc
298 K
PdCl 2
II
NMR