Vibrational studies of phosphines: Raman spectra of the phospines PMexPh3−x(x = 0−3) and normal coordinate analysis of trimethylphosphine

Pikl, R.; Duschek, Frank; Fickert, C.; Finsterer, R.; Kiefer, W.

doi:10.1016/s0924-2031(97)00007-6

Cited by 24 publications

(18 citation statements)

References 27 publications

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“…According to this approach from a maximum of 30 bands expected in this region, only 6 were found to be dependent on the substituent mass. 31,32 All bands observed in this region for the three compounds are very similar and show good agreement with those described by Whiffen and co-workers. 31,32 Below 500 cm -1 , apart from bands at 145 cm -1 and 168 cm -1 , assigned to Pd-Pd and Pd-P stretching, respectively, the spectra of the three compounds present differences.…”

Section: Raman Spectroscopysupporting

confidence: 88%

“…31,32 All bands observed in this region for the three compounds are very similar and show good agreement with those described by Whiffen and co-workers. 31,32 Below 500 cm -1 , apart from bands at 145 cm -1 and 168 cm -1 , assigned to Pd-Pd and Pd-P stretching, respectively, the spectra of the three compounds present differences. 19 For instance, bands in the region 253-284 cm -1 , that can be assigned to Pd-Cl stretching are present in the spectra of both [Pd 2 Cl 2 (dppm) 2 ] and [Pd 2 (SnCl 3 )Cl(dppm) 2 ], in contrast with the presence of bands at 207 cm -1 and 320 cm -1 assigned to Pd-Sn and Sn-Cl stretching, respectively, in the spectra of the compounds containing the SnCl 3 groups.…”

Section: Raman Spectroscopysupporting

confidence: 88%

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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: Raman Spectroscopysupporting

confidence: 88%

Section: Raman Spectroscopysupporting

confidence: 88%

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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“…[50][51][52][53] Phosphanes in general have been mainly used as protecting groups in organic synthesis as well as in catalytic processes, in which they were responsible for the decisive reaction step. [54] For this reason, PPh 3 was chosen as the second metal-binding domain in studying the surface coordination chemistry of BTAH on a Cu electrode.…”

Section: Introductionmentioning

confidence: 99%

Combined Studies on the Surface Coordination Chemistry of Benzotriazole at the Copper Electrode by Direct Electrochemical Synthesis and Surface‐Enhanced Raman Spectroscopy

Yuan¹,

Wei²,

Qin³

et al. 2007

Eur J Inorg Chem

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The surface coordination chemistry of benzotriazole (BTAH) on a Cu electrode was investigated by electrochemical synthesis of surface complexes and in situ electrochemical surface-enhanced Raman spectroscopy (SERS) in nonaqueous solution. Two different surface complexes were prepared in solution with or without triphenylphosphane (PPh 3 ). A new mixed-valence Cu-N cluster compound containing BTAH was synthesized by direct electrochemical oxidation of Cu in nonaqueous solutions with

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“…Triphenylphosphine (pph 3 ) is one of the most commonly used ligands in organometallic and coordination chemistry and is one of the most common ligands found in homogeneous transition metal catalysts for the binding and transformation of organic substrates. These ligands are used mainly as protecting groups in organic syntheses as well as in catalytic processes, where they are responsible for the decisive reaction step [30]. For this reason, pph 3 was chosen as the second metal-binding domain in studying the formation and the inhibition of BTA film.…”

Section: Introductionmentioning

confidence: 99%

Negative role of triphenylphosphine in the inhibition of benzotriazole at the Cu surface studied by surface-enhanced Raman spectroscopy

Yao¹,

Yuan²,

Gu³

2004

Journal of Electroanalytical Chemistry

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Vibrational studies of phosphines: Raman spectra of the phospines PMexPh3−x(x = 0−3) and normal coordinate analysis of trimethylphosphine

Cited by 24 publications

References 27 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

Combined Studies on the Surface Coordination Chemistry of Benzotriazole at the Copper Electrode by Direct Electrochemical Synthesis and Surface‐Enhanced Raman Spectroscopy

Negative role of triphenylphosphine in the inhibition of benzotriazole at the Cu surface studied by surface-enhanced Raman spectroscopy

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