Five-coordination in platinum(II) species: when and why

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. AbstractThe coordination chemistry of the ligand I,l'-bis(2-pyridyi)ferrocene (BPF) towards palladium and platinum has been studied. in which the ethylene is tightly coordinated to the metal centre, reacts with an additional BPF ligand to give the four.coordinated complex (BPF)PtCi 2(CH 2 = CH 2).

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“…The Pt-N and Pt-C! distances are in the range observed for other four-coordinated platinum complexes [39,[44][45][46][47].…”

Section: Molecular Structure Ofmentioning

confidence: 49%

Coordination chemistry of 1,1′-bis(2-pyridyl)ferrocene in palladium(II) and platinum(II) complexes and reaction of (BPF)Pd(Me)Cl with CO. X-ray structure of (1,1′-bis(2-pyridyl)ferrocene)Pd(Me)Cl and (1,1′-bis(2-pyridyl)ferrocene)[PtCl2(CH2  CH2)]2

Delis

Leeuwen

Vrieze

et al. 1996

Journal of Organometallic Chemistry

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“…A vacant site may be created by dissociation of one of the nitrogen donor atoms of the bidentate nitrogen ligand thereby forming intermediate V (Scheme 2). We previously have suggested that the CO insertion into the Pd-C bond of complexes containing bidentate nitrogen ligands may follow such a route, as derived from the work of Natile et al [66][67][68] and other groups, 51,69,70 who found that even with very rigid bidentate nitrogen ligands (partial) dissociation of one nitrogen donor may occur. Moreover, work done in our and other laboratories has shown that dissociation of one nitrogen donor in the complexes (2,2′-bipyrimidine)Pd(C(dNR)Me)Cl 71 and (2,2′-bipyrimidine)-Pd(η 3 -allyl)BF 4 60 occurs in solution.…”

Section: Discussionmentioning

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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“…Another surprising result was a very fast CO insertion in methanol and even in H_,O observed for the complex [ (terpy)Pd(Me) ]C1 containing the terdentate :.bonded terpy ligand [161. These accelerating effects could be rationalised by a mechanism, (1996) [87][88][89][90][91][92][93][94][95][96][97][98][99][100][101][102][103] partly based on the work of Italian groups [17][18][19][20][21][22], which involves a temporary dissociation of one nitrogen donor atom of the ligand during the substitution steps of the insertion process.…”

Section: Introductionmentioning

confidence: 99%

Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridyl)quinoline towards palladium and platinum. X-ray crystal structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)-Pd(C(O)Me)Cl and (8-(2-pyridyl)quinoline)Pd(PEt3)Cl2

Delis

Rep

Rülke

et al. 1996

Inorganica Chimica Acta

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Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridy)quinoline towards palladium and platinum. X-ray structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)Pd(C(O)Me)Cl and (8-(2-p2 Delis, J.G.P.; Rep, M.; Rulke, R.E.; van Leeuwen, P.W.N.M.; Vrieze, K.; Fraanje, J.; Goubitz, K. Published in:Inorganica Chimica Acta DOI:10.1016/S0020-1693(96)05215-2 Link to publication Citation for published version (APA):Delis, J. G. P., Rep, M., Rulke, R. E., van Leeuwen, P. W. N. M., Vrieze, K., Fraanje, J., & Goubitz, K. (1996). Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridy)quinoline towards palladium and platinum. X-ray structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)Pd(C(O)Me)Cl and (8-(2-p2. Inorganica Chimica Acta, 250, 87-103. DOI: 10.1016/S0020-1693(96)05215-2 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. AbstractThe coordination chemistry of the new bidentate nitrogen ligands 8-( 2-pyridyl)quinoline (8-PQ) and 8-(6-methyl-2-pyridyl)quinotine) (Me-8-PQ) towards palladium and platinum has been studied. Several (NnN)Pd(R)C! and (NnN)Pd(alkene) complexes have been synthesised. The complex (8-PQ)Pd(Me)CI has been characterised by a single crystal X-ray determination (crystal dat;:: triclinic space group P / with a=8.513(5), b =9.338(4), c= 10.219(2) ,~, a= 108.11(2),/3=89.g2(3), 3, = 116.81 (4) °, V=680.I (6) .~3 R=0.033, Z--2). A fast CO insertion occurs into the palladium-carbon bond of the complexes ( NnN)Pd( Me)CI providing the ( N'~N)P,J(C(O) Me)C! c~omplexes. For ( 8-PQ)Pd(C(O)Me)CI an X-ray structure determination has been carried out (crysta! data: monoclinic space group P2Jc with a=9.084(4), b= 10.179(3), c= io.400(3) ~,,/3--95.59(2) °, V= 1509.2(9) A 3. R=0.043, Z=4). Unexpecied in both molecular structures is the large dihedral angle between the plane of the bidentate nitrogen ligand and the coordination plane of the palladium. Both bidentate coordinating ligands 8-PQ and Me-8-PQ show a relatively large bite angle. A monodentate coordination mode has been observed for the complexes (N'~N)M( PEh)CI2 (M = Pd, Pt), as the pyridyl group of the iigand is coordinated to the metal while the quinoline group i...

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Five-coordination in platinum(II) species: when and why

Cited by 82 publications

References 13 publications

Coordination chemistry of 1,1′-bis(2-pyridyl)ferrocene in palladium(II) and platinum(II) complexes and reaction of (BPF)Pd(Me)Cl with CO. X-ray structure of (1,1′-bis(2-pyridyl)ferrocene)Pd(Me)Cl and (1,1′-bis(2-pyridyl)ferrocene)[PtCl2(CH2  CH2)]2

Coordination chemistry of 1,1′-bis(2-pyridyl)ferrocene in palladium(II) and platinum(II) complexes and reaction of (BPF)Pd(Me)Cl with CO. X-ray structure of (1,1′-bis(2-pyridyl)ferrocene)Pd(Me)Cl and (1,1′-bis(2-pyridyl)ferrocene)[PtCl2(CH2  CH2)]2

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

Coordination modes of the novel bifunctional nitrogen ligands 8-(2-pyridyl)quinoline and 8-(6-methyl-2-pyridyl)quinoline towards palladium and platinum. X-ray crystal structures of (8-(2-pyridyl)quinoline)Pd(Me)Cl, (8-(2-pyridyl)quinoline)-Pd(C(O)Me)Cl and (8-(2-pyridyl)quinoline)Pd(PEt3)Cl2

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