Stable Palladium(0), Palladium(II), and Platinum(II) Complexes Containing a New, Multifunctional and Hemilabile Phosphino−Imino−Pyridyl Ligand:  Synthesis, Characterization, and Reactivity

Abstract

Stable palladium(0), palladium(II) and platinum(II) complexes containing a new, multifunctional and hemilabile phosphino-imino-pyridyl ligand: Synthesis, characterization and reactivity Rulke, R.E.; Kaasjager, V.E.; Wehman, P.; Elsevier, C.J.; van Leeuwen, P.W.N.M.; Vrieze, K.; Fraanje, J.; Goubitz, K.; Spek, A.L. Published in: Organometallics DOI:10.1021/om9509047Link to publication Citation for published version (APA):Rulke, R. E., Kaasjager, V. E., Wehman, P., Elsevier, C. J., van Leeuwen, P. W. N. M., Vrieze, K., ... Spek, A. L. (1996). Stable palladium(0), palladium(II) and platinum(II) complexes containing a new, multifunctional and hemilabile phosphino-imino-pyridyl ligand: Synthesis, characterization and reactivity. Organometallics, 15, 3022-3031.

Amine-thioether and amine-pyridine complexes of palladium(II) and the reactivity of the methyl complexes towards CO and allenes

“…In analogy to recently reported insertions of (substituted) allenes into the palladium methyl bond of [ PdX(Me) (NIq) ] [30,31,33] it has been found that the complexes [PdX(Me)(L)] (L--NS) react rapidly and quantitatively to ~.fford ~/3-allylpalladium compounds (Scheme I). Cow duc~ivity experiments showed that the complexes are ionic in solution.…”

“…complexes by Gogoll etal. [47] and Vrieze and co-workers [ 30]. Therefore it was a surprise that even at low temperatures (213 K), complexes 12a, 13a, 12b.…”

“…When considering the reaction of allenes with complexes [PdCI(R)(NS)] (R--Me, C(O)Me), it is useful to note that extensive kinetic studies have shown that the reactions of alkenes like norbomadiene with [PdX(C(O)Me) (NN) ] [30] and allenes with [PdXR(NN)] (R--Me, C(O)Me) [ 30,31 ] generally have similar features and all follow hhe two-term rate law: ko~ = k t + k2 [ A ] ( A = alkene and allene). Also one should realize that the course of insertion reactions of this type is more difficult to interpret than the course of simple substitution reactions of dS-metal complexes [48], since the insertion step is proceeded by the substitution steps.…”

Synthesis and structural characterization of rhenium(I) tricarbonyl complexes with the bidentate ligands o-(diphenylphosphino)benzaldehyde (P∩O) and o-[(diphenylphosphino)benzylidene]analine (P∩N)

“…This can undoubtedly be explained by the stronger metal-to-carbonyl back-bonding in the imine phosphine complexes [37]. The appreciable coupling t o the phosphorus atom [38] exhibited by the aldehyde proton (complexes 1 and 2) and imine proton (complexes 3 and 4) expected as doublets) is the most remarkable aspect of the 1 H NMR spectra.…”

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

“…Vrieze and co-workers however, were able to separate a complex containing the PNN ligand and palladium(0) without any stabilizing coordinated olefins (naked palladium) [45]. Similar species could be employed as starting materials for the subsequent synthesis of olefin derivatives whose stability might arise from the interplay between the olefin coordinating capability and the ligand chelating effect.…”