Zhang Jumei, Li Gang, Yuan Qinqin, Zou Jinghan, Yang Dong, Zheng Huijun, Wang Chong, Yang Jianpeng, Jing Qiangshan, Liu Yanming, Fan Hongjun, Xie Hua
State Key Laboratory of Molecular Reaction Dynamics, Collaborative Innovation Center of Chemistry for Energy and Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
University of Chinese Academy of Sciences, 19A Yuquan Road, Beijing 100049, China.
J Phys Chem A. 2020 Mar 19;124(11):2264-2269. doi: 10.1021/acs.jpca.0c00313. Epub 2020 Mar 5.
A series of heteronuclear group 5 metal-nickel carbonyls MNi(CO) (M = V, Nb, Ta) have been generated via a laser ablation ion source and studied by photoelectron velocity-map imaging spectroscopy. Quantum chemical calculations have been performed to probe the electronic and geometric structures and help to assign the spectra. The adiabatic detachment energies (ADEs) and vertical detachment energies (VDEs) are deduced from spectra to be 3.40/3.58, 3.34/3.55, 3.30/3.50 eV, which are consistent with quantum chemical computational results. The MNi(CO) (M = V, Nb, Ta) consists of three bridging carbonyls, one carbonyl terminally bonded to the Ni atom and three carbonyls terminally bonded to the M (M = V, Nb, Ta) atom. These geometries are different from homobinuclear Cr(CO), Ni(CO), Pd(CO), and Fe(CO) and heterobinuclear CuFe(CO), CoZn(CO), and CO is largely activated by a bridging coordination mode. The experimental and theoretical results would provide important information to understand the chemisorbed CO molecules on alloy surfaces or interfaces, which is of great significance to elucidate CO molecule activation processes.
通过激光烧蚀离子源产生了一系列异核第5族金属-镍羰基化合物MNi(CO)（M = V、Nb、Ta），并采用光电子速度映射成像光谱进行了研究。已进行量子化学计算以探究其电子和几何结构，并辅助进行光谱归属。从光谱中推导出绝热电子亲和能（ADE）和垂直电子亲和能（VDE）分别为3.40/3.58、3.34/3.55、3.30/3.50 eV，这与量子化学计算结果一致。MNi(CO)（M = V、Nb、Ta）由三个桥连羰基、一个端基键合到Ni原子的羰基以及三个端基键合到M（M = V、Nb、Ta）原子的羰基组成。这些几何结构不同于同双核Cr(CO)、Ni(CO)、Pd(CO)和Fe(CO)以及异双核CuFe(CO)、CoZn(CO)，并且CO通过桥连配位模式在很大程度上被活化。实验和理论结果将为理解合金表面或界面上化学吸附的CO分子提供重要信息，这对于阐明CO分子的活化过程具有重要意义。
