Synthesis and molecular structures of palladium and platinum complexes of PTFA: models of Grignard cross-coupling catalysts

Jedlicka, Brigitte; Rülke, Richard E.; Weissensteiner, Walter; Fernández‐Galán, Rafael; Jalón, Félix A.; Manzano, Blanca R.; Fuente, Jerónimo Rodríguez-de la; Veldman, Nora; Kooijman, Huub; Spek, Anthony L.

doi:10.1016/0022-328x(95)06044-w

Cited by 32 publications

(23 citation statements)

References 24 publications

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“…The large majority of the Pd-P lengths lies in the proximity of 2.28 Å (2.27-2.29 Å). Again, in two cases the values of 2.34 and 2.23 Å can be found in the literature [93,94]. Owing to the p-back donation, the average Pd-P length is shorter than the Pd-S bond despite the larger atomic dimensions of the phosphorus atom.…”

Section: Complexes Bearing Mixed Bi-and Ter-dentate N-s P-s and P-n mentioning

confidence: 60%

“…In contrast with the compounds just described, hemi-labile auxiliary ligands containing phosphorus and nitrogen were more extensively studied [26,42,43,[90][91][92][93][94]. Again, irrespectively of the stabilizing olefin the bond lengths are very similar among the fourteen complexes examined with the Pd-N bond length usually spanning within 2.11 and 2.25 Å.…”

Section: Complexes Bearing Mixed Bi-and Ter-dentate N-s P-s and P-n mentioning

confidence: 99%

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

Canovese

Visentin

2010

Inorganica Chimica Acta

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a b s t r a c tAn overview of the general features of electron-poor olefin stabilized palladium(0) complexes bearing labile and hemi-labile ancillary ligands is presented. In particular, we have summarized the synthetic methodologies, the ligands commonly used, and the characterization of such complexes. The behavior of these species in solution is also described with particular attention to their fluxional rearrangements and reactivity. Thus, olefin exchange reactions are described and a comprehensive order of coordinative capability of the most widely used electron-poor alkenes is presented. The reactions of the title complexes dealing with olefin isomerization, oxidative addition, and formation of palladacyclopentadiene derivatives are eventually reported together with their main structural characteristics.

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Section: Complexes Bearing Mixed Bi-and Ter-dentate N-s P-s and P-n mentioning

confidence: 60%

Section: Complexes Bearing Mixed Bi-and Ter-dentate N-s P-s and P-n mentioning

confidence: 99%

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

Canovese

Visentin

2010

Inorganica Chimica Acta

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“…[8] The only other related structure is a methyl-substituted complex (PTFA)Pt(CH 3 )Cl [PTFA: (η 5 -cyclopentadienyl)(η 5 -4-endo- (3); the asymmetric unit also contains three benzene molecules that are not shown in this figure dimethylamino-3-diphenylphosphanyl-4,5,6,7-tetrahydro-1H-indenyl)iron]. [9] A chlorovinyl-substituted bis(phosphane)Pt II complex (Me 2 PhP) 2 Pt(CClϭCH 2 ) 2 was reported in the literature with a PtϪC bond length of 205.3(5) pm. [10] In comparison, the PtϪC bond length in 3 is rather short [PtϪC (19), 200.2(3) pm].…”

Section: Resultsmentioning

confidence: 99%

“…Complex 4 was structurally characterized and has a distorted octahedral geometry (Figure 2 and Table 3 (7) 86.1 C(2)ϪP(1)ϪC (8) 105.9(3) C(11)ϪN(10)ϪC(11)* 105.4(10) C(9)ϪN(10)ϪC (11) 87.3 (9) 206.3(10) pm; PtϪC(21): 208.2(9) pm] are in the same range as for corresponding Pt II complexes with a PϪN-chelating ligand. [14] Due to the disorder of the axial positions, an average distance of only 240.9(3) pm was found.…”

Section: Reaction Of (P ʝ N)ptme 2 With Ch 3 CLmentioning

confidence: 99%

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Stöhr

Sturmayr

Kickelbick

et al. 2002

Eur. J. Inorg. Chem.

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The complex [(κ2‐P,N)‐Ph2PCH2CH2NMe2]PtMe2 reacts with chlorinated hydrocarbons such as CCl4, CHCl3, CH2Cl2, and CH3Cl by oxidative addition of the C−Cl bond. In the reaction with CCl4, the complexes [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)Cl, [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)3Cl, and [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(CCl=CH2)Cl are obtained. The analogous P,P‐chelated complex [(κ2‐P,P)‐Ph2CH2CH2PPh2]PtMe2 does not react under the same conditions. Reaction of [(κ2‐P,N)‐Ph2PCH2CH2NMe2]PtMe2 with ClSiMe2Ph results in the formation of Ph2Me4Si2 along with [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)Cl and [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)3Cl. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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“…[11,18] The dissociative processes lead to unsaturated (or solvent-coordinated) species which may be of importance in the mechanism of the oxidative addition.…”

Section: Solution Behaviour Of the Palladium(0) And Palladium(ii) Commentioning

confidence: 99%

Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η²‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes

et al. 2004

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The complexes [Pd(η2‐dmfu)(P−N)] {dmfu = dimethyl fumarate; P−N = 2‐(PPh2)C6H4−1‐CH=NR, R = C6H4OMe‐4 (1a), CHMe2 (2a), C6H3Me2‐2,6 (3a), C6H3(CHMe2)2‐2,6 (4a)} undergo dynamic processes in solution which consist of a P−N ligand site exchange through initial rupture of the Pd−N bond at lower energy and an olefin dissociation‐association at higher energy. According to equilibrium constant values for olefin replacement, the complex [Pd(η2‐fn)(P−N)] (fn = fumaronitrile, 1b) has a greater thermodynamic stability than its dmfu analogue 1a. The kinetics of the oxidative addition of ArI (Ar = C6H4CF3‐4) to 1a and 2a lead to the products [PdI(Ar)(P−N)] (1c, 2c) and obey the rate law, kobs = k1A + k2A[ArI]. The k1A step involves oxidative addition to a reactive species [Pd(solvent)(P−N)] formed from dmfu dissociation. The k2A step is better interpreted in terms of oxidative addition to a species [Pd(η2‐dmfu)(solvent)(κ1‐P−N)] formed in a pre‐equilibrium step from Pd−N bond breaking. The complexes 1c and 2c react with PhC≡CSnBu3 in the presence of an activated olefin (ol = dmfu, fn) to yield the palladium(0) derivatives [Pd(η2‐ol)(P−N)] along with ISnBu3 and PhC≡CAr. The kinetics of the transmetallation step, which is rate‐determining for the overall reaction, obey the rate law: kobs = k2T[PhC≡CSnBu3]. The k2T values are markedly enhanced in more polar solvents such as CH3CN and DMF. The solvent effect and the activation parameters suggest an associative SE2 mechanism with substantial charge separation in the transition state. The kinetic data of the above reactions in various solvents indicate that, for the cross‐coupling of PhC≡CSnBu3 with ArI catalysed by 1a or 2a, the rate‐determining step is represented by the oxidative addition and that CH3CN is the solvent in which the highest rates are observed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Synthesis and molecular structures of palladium and platinum complexes of PTFA: models of Grignard cross-coupling catalysts

Cited by 32 publications

References 24 publications

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

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

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η²‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes

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Synthesis and molecular structures of palladium and platinum complexes of PTFA: models of Grignard cross-coupling catalysts

Cited by 32 publications

References 24 publications

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

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

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η2‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes

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Kinetic Studies of the Oxidative Addition and Transmetallation Steps Involved in the Cross‐Coupling of Alkynyl Stannanes with Aryl Iodides Catalysed by η²‐(Dimethyl fumarate)(iminophosphane)palladium(0) Complexes