Novel reactions of metal-metal bonds. Insertion of isocyanides and carbon monoxide into the palladium-palladium bond of some palladium(I) dimers

Benner, Linda S.; Balch, Alan L.

doi:10.1021/ja00487a021

Cited by 143 publications

(52 citation statements)

References 16 publications

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“…[20][21][22][23][24] In general, color changes upon gas exposure have been observed for all samples, indicating insertion of gas molecules into the Pd-Pd bonds. Evidences for the insertion reactions were provided by UV-Visible spectroscopy and after gas exposure new bands can be observed in Figure 5.…”

Section: Reactivity Of Metal-metal Bondsmentioning

confidence: 83%

“…These new bands appear at the same wavenumbers observed when the reactions are carried out in solution. [20][21][22][23][24] Additional characterization, such as Raman spectrosopy, was not possible owing to the dilute character of the Aframe adducts in the glass. However, measurements of the intensities of color change by UV-Visible spectroscopy may be the basis for use of this material in gas detection.…”

Section: Reactivity Of Metal-metal Bondsmentioning

confidence: 99%

“…Pd-Pd bond lengths were found to increase by 0.5 Å after insertion of molecules with withdrawing groups such as CO, SO 2 , methylene groups, and isocyanides. [20][21][22][23][24][25] Adducts with Aframe structures such as [Pd 2 Cl 2 (µ-SO 2 )(dppm) 2 ] and [Pd 2 Cl 2 (µ-CO)(dppm) 2 ] can be prepared by bubbling the gases into solutions of the compound [Pd 2 Cl 2 (dppm) 2 ], with observable color changes.As far as the reactivity of single bonded Pd 2 moieties are concerned attempts previously reported to immobilize similar compounds onto polystyrene for application such as separation of gases were unsuccessful due to steric demands. 25 We were further interested in studying the reactions of the immobilized species with CO and SO 2 gases, having reported preliminary results for porous Vycor glass.…”

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Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = Bis(diphenylphosphino)methane) complexes on porous vycor glass

Gimenez¹,

Alves²

2004

J. Braz. Chem. Soc.

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Neste trabalho o vidro poroso Vycor foi utilizado como matriz para a imobilização de complexos contendo ligação metal-metal [Pd 2 Cl 2 (dppm) 2 ], [Pd 2 (SnCl 3 )Cl(dppm) 2 ] e [Pd 2 (SnCl 3 ) 2 (dppm) 2 ] A elevada reatividade das ligações metal-metal em reações de inserção de moléculas como CO e SO 2 é preservada no meio poroso, sendo reversível sob vácuo. Os espectros de RMN MAS 31 P, refletância difusa no infravermelho e Raman indicaram que há uma gama de interações possíveis entre o vidro e as moléculas, como resultado da disponibilidade de diferentes grupamentos presentes nas moléculas, bem como de uma topologia porosa irregular. O caráter estático das moléculas no ambiente restrito impede movimentos do anel Pd 2 P 4 C 2 entre as conformações barco e cadeira, de modo que as moléculas confinadas podem ter diferentes conformações.Porous Vycor glass (PVG) is used as a matrix for immobilization of complexes containing metal-metal bonds: [Pd 2 Cl 2 (dppm) 2 ], [Pd 2 (SnCl 3 )Cl(dppm) 2 ] and [Pd 2 (SnCl 3 ) 2 (dppm) 2 ]. The high reactivity of the metal-metal bonds in insertion reactions with small molecules such as CO and SO 2 is preserved in the pore medium, and is reversible under vacuum.31 P MAS-NMR and Raman spectra indicate that there is a range of interactions between the glass and the adsorbed molecules as a result of the availability of different groups in the molecules and of the irregular pore topology as well. The static character of the molecules in the restrictive pore environment precludes motions such as flipping of the ring Pd 2 P 4 C 2 between boat and chair conformations and rotation of the phenyl rings, and the molecules may present a range of conformations.Keywords: palladium complexes, Vycor, immobilization, 31 P NMR, Raman, metal-metal bond IntroductionMany adsorption studies related to organometallic compounds and transition metal complexes on porous glasses have been performed with the purpose of applications such as catalysis 1,2 and formation of nanoparticles by thermal decomposition or photolysis of the molecular species. [3][4][5][6][7] In this area, a number of papers describe the immobilization of carbonyl complexes of iron 3-7 and ruthenium 8-10 onto porous glasses, since these complexes are good precursors to metallic or oxide particles via thermal and photochemical decomposition.Immobilization studies of transition metal phosphine complexes were limited for many years by the lack of suitable characterization techniques. Infrared spectroscopy is very useful in the characterization of carbonyl complexes embedded in porous glasses, giving however spectra dominated by the silica matrix bands in the case of phosphine complexes. The use of solid-state NMR techniques in addition to complementary vibrational measurements can be helpful in providing information about the structure and interactions between molecules and substrates. 15 These compounds take part in different types of reactions, such as additions, substitutions and insertions, owing to the presence of a single metal-metal b...

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Section: Reactivity Of Metal-metal Bondsmentioning

confidence: 83%

Section: Reactivity Of Metal-metal Bondsmentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = Bis(diphenylphosphino)methane) complexes on porous vycor glass

Gimenez¹,

Alves²

2004

J. Braz. Chem. Soc.

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“…Bis-(diphenylphosphino)methane (dppm), 1,2-bis(2-pyridyl)ethylene (bpe) and AgClO 4 were purchased from Aldrich and used without further purification. All organic solvents were dried by general procedures and distilled before use.…”

Section: Preparation Of Complexmentioning

confidence: 99%

Crystal Structure of Tetranuclear Palladium Complex Bridged by Bis(diphenylphosphino)methane, [Pd4(μ-dppm)4(μ-Cl)2](ClO4)2•bpe

et al. 1998

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The bidentate phosphine ligands such as bis(diphenylphosphino)methane (dppm) and 2-(diphenylphosphino)pyridine (Ph 2 Ppy) are useful bridging ligands to provide homo-and heteronuclear complexes with a close metal-metal distance. [1][2][3] A large number of polynuclear palladium complexes have been prepared using the dppm ligand, and their structures and properties have been characterized. In particular, dinuclear palladium dppm complexes readily react with relatively small molecules such as CO, SO 2 , RCN, CR 2 =CR 2 to give the dinuclear structure in A-frame mode via the insertion reaction into a Pd-Pd bond. On the other hand the investigations of the structure, property and reactivity to polynulcear palladium dppm complexes are not enough 2 owing to the difficulties of isolation and crystallization. In this study tetranuclear palladium complex [Pd 4 (m-dppm) 4 (m-Cl) 2 ](ClO 4 ) 2 ·bpe (1) was prepared and the structure was crystallographically determined. Experimental Preparation of complex 1All operations were carried out under an argon atmosphere using standard Schlenk techniques. Bis-(diphenylphosphino)methane (dppm), 1,2-bis(2-pyridyl)ethylene (bpe) and AgClO 4 were purchased from Aldrich and used without further purification. All organic solvents were dried by general procedures and distilled before use. Dinuclear palladium(I) dppm complex [Pd 2 (m-dppm) 2 Cl 2 ] was prepared according to the literature. 4 Tetranuclear palladium complex [Pd 4 (m-dppm) 4 -(m-Cl) 2 ] (ClO 4 ) 2 ·bpe (1) was synthesized according to following procedures. [Pd 2 (m-dppm) 2 Cl 2 ] (188.8 mg, 0.18 mmol) and AgClO 4 (74.6 mg, 0.36 mmol) were mixed in ethanol (30 cm 3 ) for 3 h and the resultant reddish brown suspension was filtered. The bpe ligand (66.0 mg, 0.36 mmol) was added to the filtrate and the solution was stirred for 2 h. The reddish brown solution was again filtered and the filtrate was sealed in a 5 mm diameter glass tube. The solution was allowed to stand for two weeks at ambient temperature. The reddish orange plate crystals of 1 were collected, together with a small amount of yellow needle crystals. Found: C, 55.64; H, 4.42; N,3 Data collection, structure solution and refinements of complex 1A reddish orange crystal with an approximate dimension of 0.10´0.05´0.05 mm was attached to the end of a glass fiber and mounted on a Rigaku AFC-5R diffractometer with a graphite monochromated Mo K a radiation (l=0.71069 Å). The detailed measurement conditions and the crystal data are listed in Table 1. Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range 6.67<2q<12.36˚, corresponded to those of a triclinic cell.

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11. Binuclear Transition Metal Complexes Bridged by Methylenebis(Diphenylphosphine)

Balch

Benner

Basil

1982

Inorganic Syntheses

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Novel reactions of metal-metal bonds. Insertion of isocyanides and carbon monoxide into the palladium-palladium bond of some palladium(I) dimers

Cited by 143 publications

References 16 publications

Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = Bis(diphenylphosphino)methane) complexes on porous vycor glass

Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = Bis(diphenylphosphino)methane) complexes on porous vycor glass

Crystal Structure of Tetranuclear Palladium Complex Bridged by Bis(diphenylphosphino)methane, [Pd4(μ-dppm)4(μ-Cl)2](ClO4)2•bpe

11. Binuclear Transition Metal Complexes Bridged by Methylenebis(Diphenylphosphine)

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