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

Ankersmit, Hubertus A.; Veldman, Nora; Spek, Anthony L.; Eriksen, K.; Vrieze, K.; Koten, Gerard van

doi:10.1016/s0020-1693(96)05315-7

Cited by 36 publications

(22 citation statements)

References 56 publications

(32 reference statements)

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“…Firstly, the PNS and NN'S ligands may be considered to consist of the PN [20] and NS [6] and of the NN' [5] and NS [6] building blocks, respectively, which have been investigated in some detail before. In the case of the complexes [PdX(Me) ('02-PN) ] (PN=2-(diphenylphosphino) benzylidene-S( -)-a-methyi-benzylamine) the P and N atoms are part of a rigid six-membered ring [20].…”

Section: Discussionmentioning

confidence: 99%

“…2) shows the expected square planar coordination around the metal center formed by the P (it-P( i ) = 2.240(2)/~), imine-N (it-N(2) =2.056 (6) .~) and the S (Pt-S(I) =2.363(2) ,~) donor atoms of the PNS ligand and an iodide iigand (t t-I(1) =2.5801 (6) 3.674 ( [20]. Both the methyl group on the sulfur donor, i.e.…”

Section: [Mx(l)]x (X=ci Br I); [Mfme)(l)]x (X =Cl Br L Or17mentioning

confidence: 99%

“…It was shown that the rate of insertion of CO into the Pd-Me bond of the methylpalladium complexes [PdX(Me) (D/L-th-metMe-N,S) ] was greatly enhanced by the r/2-bonded NS ligand, when compared to complexes containing bi-and terdentate nitrogen ligands [5]. In the course of these investigations we also discovered that the insertion of CO, in the Pd-Me bond of [PdCI(Me) (D/L-th-metMe-N,S) ] in the presence of H20, caused the hydrolysis of the imine bond to an amine group, resulting in the formation of the novel and unexpectedly stable complex [PdCI(C(O)Me)(L)] (L=methionine methyl ester) [ 6] in which the ligand is bidentate bonded via the amine nitrogen as well as the methionine thioether sulfur atom,…”

Section: Coordination Of the Nss' [N-(thienylidene)-l/d-meth-mentioning

confidence: 99%

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Methyl-, acetyl- and allyl-palladium and -platinum complexes containing novel terdentate PNS and NN'S ligands

Ankersmit

Veldman

Spek

et al. 1996

Inorganica Chimica Acta

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A Methyl-, Acetyl-and Allyl-palladium and -Platinum Complexes Containing Novel Terdentate PNS and NN'S Ligands Ankersmit, H.A.; Veldman, N.; Spek, A.L.; Vrieze, K.; van Koten, G. Published in:Inorganica Chimica Acta DOI:10.1016/S0020-1693(96) Link to publication Citation for published version (APA):Ankersmit, H. A., Veldman, N., Spek, A. L., Vrieze, K., & van Koten, G. (1996). A Methyl-, Acetyl-and Allylpalladium and -Platinum Complexes Containing Novel Terdentate PNS and NN'S Ligands. Inorganica Chimica Acta, 252, 339-354. DOI: 10.1016/S0020-1693(96)05333-9 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. Palladium and platinum compounds of the composition [MX(L) ]X and [M(Me)(L)]X (M =Pd, Pt; X=C1, Br, I, O3SCF3) howe boi~n prepared from the appropriate starting materials and the new ligands (L = N-[2-(diphenylphosphino)benzylidene]-L-methioniool (PNS-I), N-[ 2-(diphenylphosphino) benzylidene l-3-propylethylsuifide (PNS-2),N-{N-[ 2-(diphenylphosphino)benzylidene l-D//-,-methio-nyll-tertbutylamine (PNS-3),N-{N-[2-(pyridine)methylidene]-DIL-methionyl}-tert-butylamine (NN'S)). The single crystal X-ray deterrnination of [PtI(PNS-3)]I (3cz) (triclinic, space group PI (No.2) with a= 10.5298(9), b= 11.5584(8), c= 14.545(2) A, a=T/.368(8), /3=84.453(9), y=79.720(7) °, V= 1696.5(3) A3, Z=2, RI =0.0456, wR'2 =0.1195) showed terdentate coordination of the trifuoctional PNS-3 ligand with a six-memhered PN containing metallacycle and a six-membered NS containing metallacycle which is in a chair conformation. The square planar geometry is completed with an iodide atom, while the second iodide atom is non-coordinating. The methylpalladium and -platinum complexes may occur in solution in various isomeric forms, as an equilibrium has been observed between the ionic [ M (Me) (r/3-PNS) ] X and the neutral [ MX(Me) (,/2-PNS) ]. The ~-PNS bonded complex may occur in two conformations, i.e. with the six-membered NS containing part of the ligand in either the chair or boat form. The methyl-palladium and-platinur ~ complexes reactedslowly with CO to form the con'esponding acetyl complexes, with insertion rates which increased in the order CI < Brl < O3SCF 3-and PNS-I < PNS-2 < PNS-3 < NN'S. Complexes [ Pd (r/3-allyl) (PNS-3) ] X (X = Ci, O3SCF a ) with 2-methylallyl and l,l,2-trimeth...

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Section: Discussionmentioning

confidence: 99%

Section: [Mx(l)]x (X=ci Br I); [Mfme)(l)]x (X =Cl Br L Or17mentioning

confidence: 99%

Section: Coordination Of the Nss' [N-(thienylidene)-l/d-meth-mentioning

confidence: 99%

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Methyl-, acetyl- and allyl-palladium and -platinum complexes containing novel terdentate PNS and NN'S ligands

Ankersmit

Veldman

Spek

et al. 1996

Inorganica Chimica Acta

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“…The allylpalladium dimers [Pd(η 3 -C3H4R)Cl]2, [Pd(η 3 -C5H8R)Cl]2, and [Pd(η 3 -C 7H12R)Cl]2 were prepared by the reaction of Pd(R)Cl(COD) (R ) Me, C(O)Me; COD ) 1,5-cyclooctadiene) with propadiene, 3-methyl-1,2-butadiene (dimethylallene, DMA), and 2,4-dimethyl-2,3-pentadiene (tetramethylallene, TMA), respectively. 25 All other starting chemicals were used as commercially obtained. Silver trifluoromethanesulfonate was stored under nitrogen in the dark.…”

Section: Methodsmentioning

confidence: 99%

Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(p-anisylimino)acenaphthene

Groen¹,

Elsevier²,

Vrieze³

et al. 1996

Organometallics

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Propadiene, 3-methyl-1,2-butadiene (DMA), and 2,4-dimethyl-2,3-pentadiene (TMA) reacted via migratory insertion with both neutral and ionic Pd(R)X(p-An-BIAN) (R = Me (1), C(O)Me (2); X = Cl (a), SO3CF3 (b)) complexes, containing the rigid nitrogen ligand bis(p-anisylimino)acenaphthene (p-An-BIAN), resulting in the novel and stable allylpalladium complexes Pd(η3-C3H4R)X(p-An-BIAN) (R = Me (3), C(O)Me (6)), Pd(η3-C5H8R)X(p-An-BIAN) (R = Me (4), C(O)Me (7)), and Pd(η3-C7H12R)X(p-An-BIAN) (R = Me (5), C(O)Me (8)), respectively (X = Cl (a), SO3CF3 (b)). The neutral complexes 6a and 7a reacted with carbon monoxide to form the acylpalladium complexes Pd(C(O)C3H4C(O)Me)Cl(p-An-BIAN) (9) and Pd(C(O)C5H8C(O)Me)Cl(p-An-BIAN) (10), respectively, while the analogous trifluoromethanesulfonate complexes 6b and 7b were completely inert toward CO. Complexes 9 and 10 reacted again with propadiene and DMA, respectively, to yield the allylpalladium complexes Pd(η3-C3H4C(O)C3H4C(O)Me)Cl(p-An-BIAN) (11) and Pd(η3-C5H8C(O)C5H8C(O)Me)Cl(p-An-BIAN) (12), respectively. Also insertion of norbornadiene in complex 10 was possible, yielding the ionic complex [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]Cl (13a), which reacted with AgSO3CF3 to give [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]SO3CF3 (13b). The novel complexes 9−12 are the first isolated and fully characterized complexes formed by successive insertion reactions of carbon monoxide and allenes, while 13a is the first isolated complex containing a metal-bonded ter-oligomer of carbon monoxide, an allene, and norbornadiene. The X-ray crystal structure of 7a has been determined and shows a distorted square pyramidal geometry in which the BIAN ligand is bonded to the palladium center in an unusual asymmetric fashion (Pd−N(1) = 2.144(7) Å; Pd−N(2) = 2.600(8) Å).

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“…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.…”

Section: Citation For Published Version (Apa)mentioning

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

Cited by 36 publications

References 56 publications

Methyl-, acetyl- and allyl-palladium and -platinum complexes containing novel terdentate PNS and NN'S ligands

Methyl-, acetyl- and allyl-palladium and -platinum complexes containing novel terdentate PNS and NN'S ligands

Stepwise Successive Insertion of Carbon Monoxide and Allenes into Palladium−Carbon Bonds of Complexes Containing the Rigid Bidentate Nitrogen Ligand Bis(p-anisylimino)acenaphthene

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

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