NMR study on the coordination behavior of dissymmetric terdentate trinitrogen ligands on methylpalladium(II) compounds

Rülke, Richard E.; Ernsting, Jan Meine; Spek, Anthony L.; Elsevier, C.J.; Leeuwen, Piet W. N. M. van; Vrieze, K.

doi:10.1021/ic00077a020

Cited by 383 publications

(369 citation statements)

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“…Propadiene was purchased from Air Products, while 1,2-heptadiene, 34 (cis,cis-1,5-cyclooctadiene)Pd(Me)Cl, 35 [Pd(η 3 - 39 1,4-di-i-Pr-1,4-diaza-1,3-butadiene, 40 and 1,4-di-p-An-1,4-diaza-1,3-butadiene 40 were synthesized according to previously reported procedures.…”

Section: Methodsmentioning

confidence: 99%

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Delis¹,

Groen²,

Leeuwen³

et al. 1997

Organometallics

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The insertion reactions of the allenes propadiene and 1,2-heptadiene in the Pd-C bond of complexes (NkN)Pd(R)X Cl, Br) have been investigated. An X-ray crystal structure determination of (8-PQ)Pd{(1-3-η)-2-methylpropenyl}Cl exhibited the unexpected monodentate coordination of the nitrogen ligand. The monodentate coordination in apolar solvents and bidentate coordination in polar solvents was demonstrated by means of NOE NMR experiments. Kinetic measurements revealed that the reactions are first order in the palladium concentration and occur via an allene concentration independent and dependent pathway. Reactions of complexes containing flexible bidentate nitrogen ligands were retarded by additional free bidentate nitrogen ligand indicating that initial dissociation of a nitrogen donor is an important step in the reaction. We have strong indications that the migration of the R group to the precoordinated allene is the rate-determining step. Instead of masslaw retardation by excess X -(X ) Cl -, Br -), an enhancement of the reaction has been observed in case of the complexes (8-PQ)Pd(Me)Cl, (8-PQ)Pd(Me)Br, and (i-Pr-DAB)Pd(C(O)-Me)Cl. Flexible bidentate nitrogen ligands greatly enhance the reaction, owing to the easy formation of an accessible site on the metal center. The insertion of allenes into the Pd-C bonds of complexes containing rigid bidentate nitrogen ligands probably proceeds via initial allene association followed by either halide or nitrogen dissociation and subsequent migration of the R group to the precoordinated allene.

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Section: Methodsmentioning

confidence: 99%

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Delis¹,

Groen²,

Leeuwen³

et al. 1997

Organometallics

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“…Solvents were carefully dried and distilled prior to use or stored under an inert atmosphere, unless denoted otherwise. [ PdCI2(COD) ], [PdCI(Me)(COD)] [8] (COD=cyclo-l,5-octadiene), Pd(DBA)2 [9] (DBA=dibenzylideneacetone) and 2-diphenylphosphine-benzaldehyde [ 10] were synthesized by literature procedures, l-Phenylethylamine, 2-bromoben :aldehyde, 1,2-propadiene (allene), 3-methyl-l,2-butadiene (DMA), 2,4-dimethyl-2,3-pentadiene (TMA), l-chloro-2-butene and l-chloro-3-methyl-2-butene are commercially available and were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…Final coordinates and equivalent isotropic thermal parameters of the non-hydrogen atoms for la and 3b are given in Table 2, and for 4a in Table 3. (7) 0.6160(9) 0.020(2) 0.0076 (7) 0.6652(9) 0.021(2) 0.0178 (7) 0.6865(11) 0.030(3) 0.0981 (8) 0.6622(13) 0.036(3) 0.1684 (9) 0.6166(16) 0.046(4) 0.1598 (8) 0.5945(13) 0.034(3) 0.1701 (6) 0.5775(8) 0.013(2) 0.2054 (6) 0.4508(9) 0.021(2) 0.2870 (7) 0.4354(9) 0.024(2) 0.3364 (6) 0.5456(9) 0.022(2) 0.3037 (6) 0.6744(9) 0.020(2) 0.2209 (6) 0 …”

Section: Crystal Structure Determinationmentioning

confidence: 99%

Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

Ankersmit

Löken

Kooijman

et al. 1996

Inorganica Chimica Acta

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Methyl-, Acetyl-and Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenyl-phosphino)benzylidene-S(--)-a-methylbenzylamine LigandAnkersmit, H.A.; Loken, B.H.; Kooijman, H.; Spek, A.L.; Vrieze, K.; van Koten, G. Published in:Inorganica Chimica Acta DOI:10.1016/S0020-1693(96)05307-8 Link to publication Citation for published version (APA):Ankersmit, H. A., Loken, B. H., Kooijman, H., Spek, A. L., Vrieze, K., & van Koten, G. (1996). Methyl-, Acetyland Allyl-palladium and -Platinum Complexes Containing the Novel Chiral Phorphorous-Imine 2-(diphenylphosphino)benzylidene-S(--)-a-methyl-benzylamine Ligand. Inorganica Chimica Acta, 252, 141-155. DOI: 10.1016/S0020-1693(96)05307-8 General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. (4a) shows an analogous geometry with a chelating PN ligand, a chloride atom and a methyl group, which is positioned cis to the phosphorus atom, completes the square planar surrounding. The methylpalladium and -platinum complexes reacted with CO to give the corresponding acetyl complexes. The insertion rates increased in the order C!

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“…The syntheses of the methylpalladium complexes 2, 3, 9, and 10 have been carried out according to published methods, starting with (COD)Pd(CH3)(Cl) 11 or (COD)-Pt(CH3)(Cl). …”

Section: ′mentioning

confidence: 99%

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

Rülke¹,

Kaasjager²,

Wehman³

et al. 1996

Organometallics

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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.

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NMR study on the coordination behavior of dissymmetric terdentate trinitrogen ligands on methylpalladium(II) compounds

Cited by 383 publications

References 0 publications

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Insertions of Allenes into Palladium−Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies

Methyl-, acetyl- and allyl-palladium and -piatinum complexes containing the novel chiral phosphorus-imine 2-(diphenylphosphino)-benzylidene-S( − )-α-methyl-benzylamine ligand

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

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