The photoreduction of CO₂ catalyzed by [fac-Re(dmbpy)(CO)₃Cl] was precisely investigated through operando measurements of X-ray absorption fine structure spectroscopy (XAFS) and laser-flash FT-IR transient spectroscopy. In the early stage of the photoreaction, Re⁰-species assigned as penta-coordinated complex, [Re⁰(dmbpy)(CO)₃], appeared and a delayed rise of Re^II-species, [Re^II(dmbpy)(CO)₃CO₂] (3) / [Re^II(dmbpy)(CO)₃COOH]⁺ (3’), were observed in XAFS measurements. The valence state of Re-center in the catalytic cycle changed as Re^I → Re⁰ → Re^II to be a clear evidence of an oxidative addition of CO₂ to the Re⁰ center. In the laser-flash induced FT-IR measurements, a rise and decay of 3 followed by a delayed rise and decay of 3’ was observed. The second electron transfer from the carbon radical of TEA to 3’ induced the formation of [Re^I(dmbpy)(CO)₄]⁺ through [Re^I(dmbpy)COOH]. The rate determining step of the catalytic cycle was revealed to be the protonation process of forming 3’ from 3.

[ fac -Re(dmbpy)(CO) ₃ Cl]催化的 CO _{2 光}还原通过 X 射线吸收精细结构光谱 (XAFS) 和激光闪光 FT-IR 瞬态光谱的操作测量进行了精确研究。在光反应的早期阶段中，Re ⁰分配为五配位的配合物，[重新-species ⁰（dmbpy）（CO）₃ ]，出现和Re延迟上升^II -species，[重新^II（dmbpy）（CO ) ₃ CO ₂ ] (3) / [Re ^II (dmbpy)(CO) ₃ COOH] ⁺ ( 3')，在 XAFS 测量中观察到。催化循环中 Re-center 的价态随 Re ^I → Re ⁰ → Re ^{II 变化}，这是 CO ₂氧化加成到 Re ⁰中心的明确证据。在激光闪光诱导FT-IR测量，上升和衰减3接着延迟上升和衰减3'进行了观察。从 TEA 的碳自由基到3'的第二次电子转移诱导了 [Re ^I (dmbpy)(CO) ₄ ] ⁺通过 [Re ^I(dmbpy)COOH]。催化循环的速率决定步骤被揭示为从3形成3'的质子化过程。