15 research outputs found
Phosphenium Hydride Reduction of [(cod)MX<sub>2</sub>] (M = Pd, Pt; X = Cl, Br): Snapshots on the Way to Phosphenium Metal(0) Halides and Synthesis of Metal Nanoparticles
The
outcome of the reduction of [(cod)ÂPtX<sub>2</sub>] (X = Cl,
Br; cod = 1,5-cyclooctadiene) with N-heterocyclic phosphenium hydrides <sup>R</sup>NHP–H depends strongly on the steric demand of the <i>N</i>-aryl group R and the nature of X. Reaction of [(cod)ÂPtCl<sub>2</sub>] with <sup>Dipp</sup>NHP–H featuring bulky N-Dipp
groups produced an unprecedented monomeric phosphenium metal(0) halide
[(<sup>Dipp</sup>NHP)Â(<sup>Dipp</sup>NHP–H)ÂPtCl] stabilized
by a single phosphine ligand. The phosphenium unit exhibits a pyramidal
coordination geometry at the phosphorus atom and may according to
DFT calculations be classified as a Z-type ligand. In contrast, reaction
of [(cod)ÂPtBr<sub>2</sub>] with the sterically less protected <sup>Mes</sup>NHP–H afforded a mixture of donor-ligand free oligonuclear
complexes [{(<sup>Mes</sup>NHP)ÂPtBr}<sub><i>n</i></sub>]
(<i>n</i> = 2, 3), which are structural analogues of known
palladium complexes with ÎĽ<sub>2</sub>-bridging phosphenium
units. All reductions studied proceed via spectroscopically detectable
intermediates, several of which could be unambiguously identified
by means of multinuclear (<sup>1</sup>H, <sup>31</sup>P, <sup>195</sup>Pt) NMR spectroscopy and computational studies. The experimental
findings reveal that the phosphenium hydrides in these multistep processes
adopt a dual function as ligands and hydride transfer reagents. The
preference for the observed intricate pathways over seemingly simpler
ligand exchange processes is presumably due to kinetic reasons. The
attempt to exchange the bulky phosphine ligand in [(<sup>Dipp</sup>NHP)Â(<sup>Dipp</sup>NHP–H)ÂPtCl] by Me<sub>3</sub>P resulted
in an unexpected isomerization to a platinum(0) chlorophosphine complex
via a formal chloride migration from platinum to phosphorus, which
accentuates the electrophilic nature of the phosphenium ligand. Phosphenium
metal(0) halides of platinum further show a surprising thermal stability,
whereas the palladium complexes easily disintegrate upon gentle heating
in dimethyl sulfoxide to yield metal nanoparticles, which were characterized
by TEM and XRD studies
A Comparative Experimental and Computational Study of Heterometallic Fe-M (M = Cu, Ag, Au) Carbonyl Clusters Containing N-Heterocyclic Carbene Ligands
The [Fe(CO)4{M(NHC)}]\u2013 (M = Cu, NHC = IMes, 1; M = Cu, NHC = IPr, 2; M = Ag, NHC = IMes, 3; M = Ag, NHC = IPr, 4; IMes = C3N2H2(C6H2Me3)2; IPr = C3N2H2(C6H3iPr2)2) mono-anions were obtained from the reaction of Na2[Fe(CO)4]\ub72thf with one equivalent of M(NHC)Cl (M = Cu, Ag; NHC = IMes, IPr) in dmso. Furthermore, the reaction of Na2[Fe(CO)4]\ub72thf with two equivalents of M(NHC)Cl in thf afforded the neutral compounds Fe(CO)4{M(NHC)}2 (M = Cu, NHC = IMes, 11; M = Cu, NHC = IPr, 12; M = Ag, NHC = IMes, 13; M = Ag, NHC = IPr, 14). 2 and 4 further reacted with one equivalent of M(IPr)Cl (M = Cu, Ag, Au) resulting in the trimetallic clusters Fe(CO)4{Cu(IPr)}{Ag(IPr)} (18), Fe(CO)4{Cu(IPr)}{Au(IPr)} (19), and Fe(CO)4{Ag(IPr)}{Au(IPr)} (20). 1-4, 11-14 and 18-20 have been spectroscopically characterized by IR, 1H and13C{1H} NMR techniques. The molecular structures of 2, 12, 18, 19 and 20 have been determined through single crystal X-ray diffraction. The structure, bonding and stability of the copper and silver IMes derivatives were compared to the related Fe-Au clusters previously reported on the basis of theoretical calculations. Stability of the Fe-M bonds decreases in the order Au > Cu > Ag, and the same trend was found for what concerns the M-IMes interactions. The decomposition products of 1-4, 11-14 and 18-20 have been studied allowing, among the others, the structural characterization of the new species [Fe2(CO)8{Ag(IPr)}]\u2013 (10) and Fe(CO)4(CH2IMes) (21)