Beckman Institute, California Institute of Technology, Pasadena, California 91125, United States.
J Am Chem Soc. 2010 Dec 1;132(47):16774-6. doi: 10.1021/ja109351h. Epub 2010 Nov 10.
Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged Co(I)-diglyoxime complex, forming Co(III)H, was monitored via transient absorption. The second-order rate constant for Co(III)H formation is in the range (3.5-4.7) × 10(9) M(-1) s(-1), with proton transfer coupled to excited-state deactivation of the photoacid. Co(III)H is subsequently reduced by excess Co(I)-diglyoxime in solution to produce Co(II)H (k(red) = 9.2 × 10(6) M(-1) s(-1)), which is then protonated to yield Co(II)-diglyoxime and H(2).
通过瞬态吸收监测到溴代萘酚三重态激发态向二氟硼桥联 Co(I)-双乙二肟配合物的质子转移，形成 Co(III)H。Co(III)H 的形成的二级速率常数在（3.5-4.7）×10(9) M(-1) s(-1)范围内，质子转移与光酸的激发态失活偶联。Co(III)H 随后在溶液中被过量的 Co(I)-双乙二肟还原为 Co(II)H（k(red) = 9.2×10(6) M(-1) s(-1)），然后质子化生成 Co(II)-双乙二肟和 H(2)。
