Stereoelectronic Effects in Cl<sub>2</sub> Elimination from Binuclear Pt(III) Complexes [electronic resource]

 0 Người đánh giá. Xếp hạng trung bình 0

Tác giả:

Ngôn ngữ: eng

Ký hiệu phân loại: 541.36 Thermochemistry and thermodynamics

Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2016

Mô tả vật lý: Size: p. 11815-11820 : , digital, PDF file.

Bộ sưu tập: Metadata

ID: 257359

Halogen photoelimination is the critical energy-storing step of metal-catalyzed HX-splitting photocycles. Homo- and heterobimetallic Pt(III) complexes display among the highest quantum efficiencies for halogen elimination reactions. Herein, we examine in detail the mechanism and energetics of halogen elimination from a family of binuclear Pt(III) complexes featuring meridionally coordinated Pt(III) trichlorides. Transient absorption spectroscopy, steady-state photocrystallography, and far-infrared vibrational spectroscopy suggest a halogen elimination mechanism that proceeds via two sequential halogen-atom-extrusion steps. Solution-phase calorimetry experiments of the meridional complexes have defined the thermodynamics of halogen elimination, which show a decrease in the photoelimination quantum efficiency with an increase in the thermochemically defined Pt?X bond strength. Conversely, when compared to an isomeric facial Pt(III) trichloride, a much more efficient photoelimination is observed for the fac isomer than would be predicted based on thermochemistry. Here, this difference in the fac vs mer isomer photochemistry highlights the importance of stereochemistry on halogen elimination efficiency and points to a mechanism-based strategy for achieving halogen elimination reactions that are both efficient and energy storing.
Tạo bộ sưu tập với mã QR

THƯ VIỆN - TRƯỜNG ĐẠI HỌC CÔNG NGHỆ TP.HCM

ĐT: (028) 71010608 | Email: tt.thuvien@hutech.edu.vn

Copyright @2024 THƯ VIỆN HUTECH