52564-36-0Relevant academic research and scientific papers
Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
Hwang, Seung Jun,Powers, David C.,Maher, Andrew G.,Anderson, Bryce L.,Hadt, Ryan G.,Zheng, Shao-Liang,Chen, Yu-Sheng,Nocera, Daniel G.
, p. 6472 - 6475 (2015)
Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing ancillary ligands to promote elimination offers a strategy to circumvent the inherently short-lived excited states of 3d metal complexes for the activation of thermodynamically challenging bonds.
Halogen Photoelimination from Monomeric Nickel(III) Complexes Enabled by the Secondary Coordination Sphere
Hwang, Seung Jun,Anderson, Bryce L.,Powers, David C.,Maher, Andrew G.,Hadt, Ryan G.,Nocera, Daniel G.
, p. 4766 - 4774 (2015/10/28)
Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.
