Dancing of Palladacycles around a “Juggler” 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand in a Trinuclear Pd(II) Complex

Vicente, José; Chicote, Mariá‐Teresa; Martínez‐Viviente, Eloísa; Martínez-Martínez, † and Antonio J.; Jones, Peter G.

doi:10.1021/ic0620440

Cited by 6 publications

(23 citation statements)

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“…The crystal structure of 7b 3 CH 2 Cl 2 has been reported in a preliminary communication. 22 Crystal data and refinement details are shown in Table 1. Intensity measurements were recorded using monochromated Mo KR radiation on a Siemens P4 (1) or SMART 1000 diffractometer.…”

Section: Methodsmentioning

confidence: 99%

“…We have already reported the activation parameters for this process and suggested a possible mechanism. 22 In this paper we put these results into context with the complete DNMR investigation of the behavior in solution of the mono-, di-, and trinuclear Pd(II) complexes.…”

Section: Introductionmentioning

confidence: 99%

“…6b and 7b22 were prepared following the methods reported in the literature. Chemical shifts are referenced to TMS ( 1 H, 13 C{ 1 H}) or H 3 PO 4 ( 31 P{ 1 H}).…”

mentioning

confidence: 99%

“…Some of these spectra are reproduced in the Supporting Information. The phase-sensitive 1 H-NOESY measurements were carried out with mixing times D8 = 600 ms-1 s. The VT NMR studies of 7b have been reported 22. The details of the calculation of the activation parameters can be found in the Supporting Information.…”

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confidence: 99%

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2-(Aminomethyl)phenyl Complexes of Au(III), Mixed Au(III)/Ag(I), and Pd(II) with the 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand: Dancing of Palladacycles around a Juggler Ligand

et al. 2010

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The reaction of [Tl(2){mu-S,S-S(2)C=C{C(O)Me}(2)}] with [Au(C,N-C(6)H(4)CH(2)NMe(2)-2)Cl(2)] (1:1) gives [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{S,S-S(2)C=C{C(O)Me}(2)}] (1) which, in turn, reacts with AgClO(4) (1:1) to give [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(OClO(3))}{S(2)C=C{C(O)Me}(2)}] (2). Complexes [{Au(C,N-C(6)H(4)CH(2)NMe(2)-2)}{Ag(X)(PPh(3))}{S(2)C=C{C(O)Me}(2)}] [X = OClO(3) (3), ONO(2) (4)] have been obtained by reaction of 1 with PPh(3) and AgClO(4) or AgNO(3), respectively (1:1:1). Complex 3 can also be obtained by reacting 2 with PPh(3) (1:1). Complexes [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(mu-Cl)](2) (R = Me, H) react (i) with [Tl(2){S(2)C=C{C(O)Me}(2)}] and [PPN]Cl (0.5:1:1, PPN = Ph(3)P=N=PPh(3)) to form PPN[Pd(C,N-C(6)H(4)CH(2)NR(2)-2){S,S-S(2)C=C{C(O)Me}(2)}] [R = H (5a), Me (5b)], or (ii) with [Tl(2){S(2)C=C{C(O)Me}(2)}] (1:1) to form [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(2){mu-S,S,O-S(2)C=C{C(O)Me}(2)}] [R = H (6a), Me (6b)]. The trinuclear complexes [{Pd(C,N-C(6)H(4)CH(2)NR(2)-2)}(3){mu(3)-O,S,S,O-S(2)C=C{C(O)Me}(2)}]ClO(4) [R = H (7a), Me (7b)] can be prepared by reacting the corresponding dinuclear complex 6a or 6b with [Pd(C,N-C(6)H(4)CH(2)NR(2)-2)(NCMe)(2)]ClO(4) (1:1). The crystal structures of 1, 6b x CH(2)Cl(2), and 7b x CH(2)Cl(2) have been determined. NMR studies have been carried out to explain the solution behavior of these complexes. VT-NMR and line shape analysis for the species where R = Me (5b, 6b, 7b) have allowed the estimation of the activation parameters for these exchange processes.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…6b and 7b22 were prepared following the methods reported in the literature. Chemical shifts are referenced to TMS ( 1 H, 13 C{ 1 H}) or H 3 PO 4 ( 31 P{ 1 H}).…”

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2-(Aminomethyl)phenyl Complexes of Au(III), Mixed Au(III)/Ag(I), and Pd(II) with the 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand: Dancing of Palladacycles around a Juggler Ligand

et al. 2010

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“…74 A trinuclear complex containing a m 3 -1,1-ethylenedithiolato ligand has been prepared with an unusual anionic carbon s-donor and shows an unprecedented fluxional behaviour with the three palladacycles exchanging around the dithiolene. 75 In addition an unprecedented formation of selenido-bridged trinuclear clusters [M 3 (m 3 -Se) 2 (L) 3 ] 2+ [M = Pd 2+ or Pt 2+ , L = dppm, dppe, dppp, (P n Pr 3 ) 2 ] via C-Se bond cleavage have been reported. 76 Organometallic A detailed consideration of azobenzenes and heteroaromatic nitrogen cyclopalladated complexes has been published.…”

Section: Coordination Chemistrymentioning

confidence: 99%

Nickel, palladium and platinum

Fletcher¹

2007

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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A Coordination Controlled Aryl–Halide Oxidative Addition to Platinum

Zenkina¹,

Karton²,

Shimon³

et al. 2009

Chemistry A European J

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Aryl À halide bond activation and coordination of unsaturated substrates are key steps in many metal-mediated carbonÀcarbon bond-forming reactions. [1, 2] Numerous experimental and computational studies have been reported on these processes.[3] The electronic nature of the reactants is known to affect both steps. In particular, an electron withdrawing group (EWG: e.g., CF 3 , CN, NO 2 ) makes the C aryl À halogen bond more ionic, weakens this bond, and therefore increases the rate of the bond activation (Scheme 1, x = 0). [4] Such EWGs strengthen metalÀolefin bonds by increasing the p-backbonding between the metal center and the carbon À carbon double bond of the substrate.[5] How would the activation of aryl À halide bonds be affected if the same substrate also contains a carbon À carbon double bond capable of interacting with a metal center (Scheme 1, x = 1)? We have shown that halogenated arylarenes are versatile systems ideal for studying coordination chemistry coupled with aryl-bond activation. For instance, the reaction of MA C H T U N G T R E N N U N G (PEt 3 ) 4 (M = Ni, Pt) with a halogenated substrate results in h 2 -coordination to a -C=C-or -N=N-moiety, followed by "ringwalking" of the metal center, yielding the product of arylÀ halide oxidative addition. [6][7][8] However, partially fluorinated substrates kinetically prefer aryl À halide bond activation. [9] Thus, the metal center can be selectively directed to a specific site by varying the electronic properties of the reactants.We observe in the stilbene systems presented here that h 2 -coordination of the platinum center to a -C=C-unit is kinetically preferable over metal insertion into the carbonÀhalide bond regardless of the electronic properties of the substrate (Schemes 1 and 2). Nevertheless, the substituents of the stilbenes play a dominant role in the overall process. The reactivity trend is opposite from that of other aryl halides: The substrates with electron-deficient substituents are transformed much slower in the products of arylÀbromide activation than in those with electron-donation groups (EDGs). The overall reactivity is controlled by the coordination of the ligand to the metal center, whereas the activation of the aryl À Br bond is the rate-determining step. These findings are in good agreement with DFT calculations.A series of reactions with stilbenes 1-7 and PtA C H T U N G T R E N N U N G (PEt 3 ) 4 were used to explore the role of substrate coordination on arylÀhalide activation. Reaction of a stoichiometric amount of PtA C H T U N G T R E N N U N G (PEt 3 ) 4 with a stilbene (1-7) in THF results in the formation of complexes 8-14, respectively, by h 2 -coordination of the metal center to the central carbon À carbon double bond (see the Supporting Information for details). No products indicative of aryl À halide bond activation were observed by 1 H and 31 P{ 1 H} NMR spectroscopy prior to the formation of these complexes. The complexes 8-14 were characterized by NMR spectroscopy. In addition, complexes 9-12 and 14 were iso...

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Dancing of Palladacycles around a “Juggler” 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand in a Trinuclear Pd(II) Complex

Cited by 6 publications

References 23 publications

2-(Aminomethyl)phenyl Complexes of Au(III), Mixed Au(III)/Ag(I), and Pd(II) with the 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand: Dancing of Palladacycles around a Juggler Ligand

2-(Aminomethyl)phenyl Complexes of Au(III), Mixed Au(III)/Ag(I), and Pd(II) with the 2,2-Diacetyl-1,1-Ethylenedithiolato Ligand: Dancing of Palladacycles around a Juggler Ligand

Nickel, palladium and platinum

A Coordination Controlled Aryl–Halide Oxidative Addition to Platinum

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