Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes

CORC > 沈阳自动化研究所 > 中国科学院沈阳自动化研究所 > 广州中国科学院沈阳自动化研究所分所

	Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes
	Han, Yulun; Kilin, Dmitri S.; May, P. Stanley; Berry, Mary T.; Meng QG(孟庆国)
刊名	Organometallics
	2016
卷号	35 期号:20 页码:3461-3473
ISSN号	0276-7333
通讯作者	Berry, Mary T. ; 孟庆国
产权排序	3
中文摘要	Photofragmentation mechanisms of gas-phase lanthanide tris(isopropylcyclopentadienyl) complexes, Ln(iCp)3, were studied through experimental photoionization time-of-flight mass spectrometry (PI-TOF-MS). A DFT-based time-dependent excited-state molecular dynamics (TDESMD) algorithm, under standard approximations, was used to simulate the photofragmentation process. Two competing reaction pathways, intact ligand stripping and ligand cracking within the metal-ligand complex, were hypothesized based on experimental data. It was evident that intramolecular hydrogen, methyl, and isopropyl abstraction play an important role in the ligand-cracking reaction pathway, leading to metal carbide and metal hydrocarbide products. The TDESMD simulations also produced branching reaction pathways for ligand ejection and ligand cracking and further suggested that both pathways are initiated by ligand-to-metal charge transfer. Although the simulations reproduced several of the proposed reactions and several of the products of cracking observed in the PI-TOF mass spectra, differences between the simulation and experimental results suggest specific directions for improvement in the computational model.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Inorganic & Nuclear ; Chemistry, Organic
研究领域[WOS]	Chemistry
关键词[WOS]	OXIDE THIN-FILMS ; ATOMIC LAYER DEPOSITION ; CHEMICAL-VAPOR-DEPOSITION ; STATE MOLECULAR-DYNAMICS ; GATE DIELECTRICS ; PHOTODISSOCIATION ; CYCLOPENTADIENYL ; CHEMISTRY ; PRECURSORS ; DECOMPOSITION
收录类别	SCI ; EI
语种	英语
WOS记录号	WOS:000386314800008
内容类型	期刊论文
源URL	[http://ir.sia.cn/handle/173321/19370]
专题	沈阳自动化研究所_广州中国科学院沈阳自动化研究所分所
推荐引用方式 GB/T 7714	Han, Yulun,Kilin, Dmitri S.,May, P. Stanley,et al. Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes[J]. Organometallics,2016,35(20):3461-3473.
APA	Han, Yulun,Kilin, Dmitri S.,May, P. Stanley,Berry, Mary T.,&Meng QG.(2016).Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes.Organometallics,35(20),3461-3473.
MLA	Han, Yulun,et al."Photofragmentation Pathways for Gas-Phase Lanthanide Tris(isopropylcyclopentadienyl) Complexes".Organometallics 35.20(2016):3461-3473.