%0 Generic
%A Oberbeckmann-Winter, Nicola
%A Braunstein, Pierre
%A Welter, Richard
%D 2005
%T Palladium Phosphino-Iminolate Complexes as
Metalloligands for Coinage Metals: A Versatile,
Ambivalent Behavior‡
%U https://acs.figshare.com/articles/dataset/Palladium_Phosphino_Iminolate_Complexes_as_Metalloligands_for_Coinage_Metals_A_Versatile_Ambivalent_Behavior_sup_sup_/3281494
%R 10.1021/om050156d.s007
%2 https://acs.figshare.com/ndownloader/files/5119237
%K dative bond
%K BF 4
%K electrophilic complexes
%K Pd
%K 10 metal center
%K iminolate N atom
%K complexes 2
%K NC
%K CH
%K coinage metal
%K nitrogen atom
%K CF
%K covalent interaction
%K Double substitution
%K coinage metals
%K heterobimetallic complexes
%K OTf
%K electrophilic metal reagent
%K orthometalated dimethylbenzylamine
%X Reactivity studies with the bis-chelated Pd(II) phosphino-iminolate complex [Pd(dmba)(κ2-P,O-PPh2NC(O)Me)] (2) (dmba = orthometalated dimethylbenzylamine) have shown
that it readily reacts as a metalloligand with electrophilic complexes of the coinage metals,
selectively via the nitrogen atom of the P,O chelate. After examining its reaction with AgOTf
(OTf = SO3CF3), which afforded the first 1-D coordination polymer containing Ag−Pd bonds,
[{Ag(2)}OTf]n (3·OTf), we have examined and compared its reactions with H+, Au(PPh3)+,
[AuCl(THT)], [Au(THT)]BF4, and [Cu(NCMe)4]BF4. Depending on the nature of the electrophilic metal reagent used, the interaction between the iminolate N atom of 2 and the
electrophile can be formally described as a dative bond involving its lone pair, which would
formally place the positive charge of the complex more on the coinage metal, or as a more covalent interaction resulting in an increased carbon−oxygen bond order and thus in the pos/baitive charge being more localized on the Pd(II) center. In the former case, the metalloligand
formally behaves as a two-electron, L-type donor, whereas in the latter, as a one-electron,
X-type donor ligand. This ambivalent behavior explains the formation of the heterobimetallic
complexes (6) and ([Au(PPh3)(2)]OTf) or
(7·BF4), respectively. Double substitution of the d10 metal center by 2 afforded the Pd/Au/Pd and Pd/Cu/Pd heterotrinuclear complexes
(8·BF4) and (9·BF4), respectively. The complexes
2, 5·OTf, 6, 7·BF4, 8·BF4·2CH2Cl2, and 9·BF4 have been structurally characterized by X-ray
diffraction.
%I ACS Publications