Thermal and photochemical reactions of triruthenium dodecacarbonyl adsorbed onto porous Vycor glass

Dieter, T.; Gafney, Harry D.

doi:10.1021/ic00283a014

Cited by 11 publications

(4 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…UV−visible spectra were recorded on an AVIV UV−vis−NIR spectrophotometer. Diffuse reflectance FTIR (DRIFT) spectra of crushed (320 mesh) impregnated PVG samples, diluted 1:30 with KBr, were recorded on a Nicolet Analytical Instruments model 20/5DX FTIR spectrometer . Raman spectra were recorded on a previously described spectrometer using 514.5 nm excitation .…”

Section: Methodsmentioning

confidence: 99%

Photochemistry of Trimethyltin Iodide in Polar Media: Orbital Parentage and Observed Reactivity

et al. 2001

Self Cite

View full text Add to dashboard Cite

(CH(3))(3)SnI exists as individual tetrahedral molecules in hexane but reacts with the silanol moieties present on the surface of porous glass and with the hydroxyl group of ethanol and hexanol to form five-coordinate adducts. With the exception of slight shifts to higher energy, formation of the adduct has little effect on the electronic spectrum of the complex, and the wavelength and O(2) dependencies of the quantum yield of (CH(3))(3)SnI disappearance indicate that the photochemistry of the complex initiates from the ligand-to-metal charge-transfer (LMCT) state populated on absorption in each medium. Nevertheless, 254 nm excitation in hexane leads to I(2) and ((CH(3))(3)Sn)(2), whereas excitation of the five-coordinate adduct on the glass surface leads to I(2), I(3)(-), ((CH(3))(3)Sn)(2), and (CH(3))(3)Sn-OSi[triple bond](OSi[triple bond]represents a surface siloxyl), while in ethanol, I(3)(-) is the only detectable product. Regardless of the medium, the ground state is polarized and population of the LMCT state creates a more uniform charge distribution from which homolytic cleavage of the (CH(3))(3)Sn-I bond is the dominant reaction pathway in each medium. In hexane, the (CH(3))(3)Sn(*) and I(*) radicals couple to form ((CH(3))(3)Sn)(2) and I(2), whereas adsorbed onto the glass, a fraction of the radical pairs thermalize via electron transfer to form I(3)(-) and a surface-bound (CH(3))(3)Sn-OSi[triple bond] species. In ethanol, excitation of the solvent adduct (CH(3))(3)Sn-OHC(2)H(5) leads to homolytic cleavage and I(2) formation, which reacts thermally with (CH(3))(3)Sn-OHC(2)H(5) to form an [(CH(3))(3)Sn(+), I(3)(-)] ion pair.

show abstract

Section: Methodsmentioning

confidence: 99%

Photochemistry of Trimethyltin Iodide in Polar Media: Orbital Parentage and Observed Reactivity

et al. 2001

Self Cite

View full text Add to dashboard Cite

show abstract

“…Using a quite different approach, Gafney and coworkers (9)(10)(11) found that metal carbonyls could be adsorbed onto flat plates of PVG (transparent surfacehydroxylated glass with a random array of interconnected cavities) through vapor deposition or by soaking in a solution of dilute carbonyl. Exposure to UV light results in the loss of a carbonyl ligand from the glass absorbed complex as illustrated by eq 1.…”

Section: Inorganic Materials Used In Lithographymentioning

confidence: 99%

“…This work follows the initial work of Wrighton's group (8) demonstrating that surface-confined organometallic complexes maintained their photochemical reactivity. Gafney and co-workers (9)(10)(11) have examined the photochemistry of metal carbonyls (Fe, Ru, group 6B) adsorbed into the bulk structure of porous Vycor glass (PVG), and quite recently, we have used a mixed-valent Fe-Pt inorganic polymer to generate mul-tiple spatially resolved surface species on optically transparent indium tin oxide (ITO) electrode surfaces (12).…”

mentioning

confidence: 99%

Inorganic Photolithography: Interfacial Multicomponent Pattern Generation

Bocarsly

Chang

et al. 1997

J. Chem. Educ.

View full text Add to dashboard Cite

“…[3][4][5][6][7] In this area, a number of papers describe the immobilization of carbonyl complexes of iron [3][4][5][6][7] and ruthenium [8][9][10] onto porous glasses, since these complexes are good precursors to metallic or oxide particles via thermal and photochemical decomposition.…”

Section: Introductionmentioning

confidence: 99%

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

Gimenez¹,

Alves²

2004

J. Braz. Chem. Soc.

View full text Add to dashboard Cite

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...

show abstract

Thermal and photochemical reactions of triruthenium dodecacarbonyl adsorbed onto porous Vycor glass

Cited by 11 publications

References 6 publications

Photochemistry of Trimethyltin Iodide in Polar Media: Orbital Parentage and Observed Reactivity

Photochemistry of Trimethyltin Iodide in Polar Media: Orbital Parentage and Observed Reactivity

Inorganic Photolithography: Interfacial Multicomponent Pattern Generation

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

Contact Info

Product

Resources

About