Structures of Vinylstannane (Ethenylstannane) and Allylstannane (2-Propenylstannane) Determined by Gas-Phase Electron Diffraction and Quantum Chemical Calculations

Strenalyuk, Tatyana; Samdal, Svein; Møllendal, Harald; Guillemin, Jean‐Claude

doi:10.1021/om0601549

Cited by 15 publications

(9 citation statements)

References 31 publications

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“…Allyltin trichloride was synthesized through the previously published route. 61 Phenyltin trichloride was purchased from Gelest and all other reagents were purchased from Sigma Aldrich. All reagents were used as received unless otherwise specified.…”

Section: Experimental Methodsmentioning

confidence: 99%

“…18 Allyltin trichloride was synthesized through a previously published route; phenyl and butyltin trichlorides were purchased. 61 Our first attempts to synthesize the organostannoic acid, followed by dehydration to make the cluster ( Figure 7A). Initial attempts with phenyltin trichloride, however, only yielded insoluble white solid (probably tin(IV) oxide due to hydrolysis of the phenyl-tin bond).…”

Section: Homolytic Cleavage Of the Tin-carbon Bondmentioning

confidence: 99%

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EUV resists based on tin-oxo clusters

Cardineau

Al-Mashat

et al. 2014

SPIE Proceedings

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We have studied the photolysis of tin clusters of the type [(RSn) 12 O 14 (OH) 6 ] X 2 using extreme ultraviolet (EUV, 13.5 nm) light, and developed these clusters into novel high-resolution photoresists. A thin film of [(BuSn) 12 O 14 (OH) 6 ][p-toluenesulfonate] 2 (1) was prepared by spin coating a solution of (1) in 2-butanone onto a silicon wafer. Exposure to EUV light caused the compound (1) to be converted into a substance that was markedly less soluble in aqueous isopropanol. To optimize the EUV lithographic performance of resists using tin-oxo clusters, and to gain insight into the mechanism of their photochemical reactions, we prepared several compounds based on [(RSn) 12 O 14 (OH) 6 ] X 2. The sensitivity of tin-oxide films to EUV light were studied as a function of variations in the structure of the counter-anions (X, primarily carboxylates) and organic ligands bound to tin (R). Correlations were sought between the EUV sensitivity of these complexes vs. the strength of the carbon-carboxylate bonds in the counteranions and vs. the strength of the carbon-tin bonds. No correlation was observed between the strength of the carboncarboxylate bonds in the counter-anions (X) and the EUV photosensitivity. However, the EUV sensitivity of the tinoxide films appears to be well-correlated with the strength of the carbon-tin bonds. We hypothesize this correlation indicates a mechanism of carbon-tin bond homolysis during exposure. Using these tin clusters, 18-nm lines were printed showcasing the high resolution capabilities of these materials as photoresists for EUV lithography.

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Section: Experimental Methodsmentioning

confidence: 99%

Section: Homolytic Cleavage Of the Tin-carbon Bondmentioning

confidence: 99%

EUV resists based on tin-oxo clusters

Cardineau

Al-Mashat

et al. 2014

SPIE Proceedings

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“…The cc-pVTZ-PP(Sn) basis set on the Sn atom has been tested for small organotin molecules, 38,39 where generally good agreement between calculated and experimental structures was obtained. However, there are indications that the bond lengths to the Sn atom are calculated to be too short.…”

Section: Methodsmentioning

confidence: 99%

Molecular Structure of Phthalocyaninatotin(II) Studied by Gas-Phase Electron Diffraction and High-Level Quantum Chemical Calculations

2008

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The molecular structure of phthalocyaninatotin(II), Sn(II)Pc, is determined by density functional theory (DFT/B3LYP) calculations using various basis sets and gas-phase electron diffraction (GED). The quantum chemical calculations show that Sn(II)Pc has C4V symmetry, and this symmetry is consistent with the structure obtained by GED at 427 degrees C. GED locates the Sn atom at h(Sn) ) 112.8(48) pm above the plane defined by the four isoindole N atoms, and a N-Sn bond length of 226.0(10) pm is obtained. Calculation at the B3LYP/ccpVTZ/cc-pVTZ-PP(Sn) level of theory gives h(Sn) ) 114.2 pm and a N-Sn bond length of 229.4 pm. The phthalocyanine (Pc) macrocycle has a slightly nonplanar structure. Generally, the GED results are in good agreement with the X-ray structures and with the computed structure; however, the comparability between these three methods has been questioned. The N-Sn bond lengths determined by GED and X-ray are significantly shorter than those from the B3LYP predictions. Similar trends have been found for C-Sn bonds for conjugated organometallic tin compounds. Computed vibrational frequencies give five low frequencies in the range of 18-54 cm-1, which indicates a flexible molecule.

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Section: Introductionmentioning

confidence: 99%

“…At present, in addition to experimental studies on the structure of tin coordination complexes, quantum chemical calculations can also give a detailed insight into coordination around Sn in such complexes. [26][27][28] Moreover, theoretical methods are a powerful tool for finding relationships between the electronic structure of complexes and their coordination patterns and, in consequence, their physicochemical properties. [26,29,30] However, in contrast to the aforementioned numerous experimental studies of SnX n (n = 2, 4) complexes with py, merely a few computational studies have been devoted to such complexes.…”

Section: Introductionmentioning

confidence: 99%

N → Sn coordination in the complexes of tin halides with pyridine: A comparison between Sn(II) and Sn(IV)

Matczak

2019

Applied Organom Chemis

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The experimentally well‐known complexation of tin(II) and tin(IV) halides with pyridine (py) leads to structures showing N → Sn coordination. In the present work, the complexes SnXn·mpy (where X = F, Cl, Br, I; n = 2, 4; m = 1, 2) possessing this kind of coordination were studied using a computational quantum chemical approach. Various aspects in the theoretical picture of these complexes were examined to find similarities and differences in their N → Sn coordination. The aspects included, among others, the physical nature of intermolecular interactions, and their role in establishing the structure and energetic stabilization of the complexes. In this context, the effect of tin valency was inspected in great detail. As proven by several theoretical methods, a largely ionic character with a certain covalent component can be attributed to the studied N → Sn coordination, irrespective of tin valency. All complexes are destabilized by py‐py and three‐body interactions, but the Sn(II) complexes experience it to a greater extent. Marked differences are observed in the structural behavior of N → Sn and SnXn during complex formation. This affects the energetics of complexation and, in consequence, the penta‐coordinated Sn(IV) center shows a higher propensity to expand its coordination number, compared with the tri‐coordinated Sn(II) center. The present study supplements the experimental characterization of SnXn·mpy and, in general, it sheds light on the coordination of heteroaromatic nitrogen to tin. The survey of the Cambridge Structural Database revealed that such coordination occurred in a number of crystal structures.

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Structures of Vinylstannane (Ethenylstannane) and Allylstannane (2-Propenylstannane) Determined by Gas-Phase Electron Diffraction and Quantum Chemical Calculations

Abstract: International audienc

Cited by 15 publications

References 31 publications

EUV resists based on tin-oxo clusters

EUV resists based on tin-oxo clusters

Molecular Structure of Phthalocyaninatotin(II) Studied by Gas-Phase Electron Diffraction and High-Level Quantum Chemical Calculations

N → Sn coordination in the complexes of tin halides with pyridine: A comparison between Sn(II) and Sn(IV)

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