Exceedingly Facile Ph-X Activation (X = Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms.
Exceedingly Facile Ph-X Activation (X = Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms.
复制标题
DOI：
10.1002/anie.201501996
复制
发表时间：
2015-07-13
影响因子：
16.6
通讯作者：
Grushin, Vladimir V.
中科院分区：
文献类型：
--
作者：
Miloserdov, Fedor M.;McKay, David;Munoz, Bianca K.;Samouei, Hamidreza;Macgregor, Stuart A.;Grushin, Vladimir V.
[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph—X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph—I bond cleavage with the just‐produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still‐present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2‐PhI intermediate, and Ph—I oxidative addition.
登录
查看更多内容
影响因子：
15
作者：
Zhang J;Bellomo A;Trongsiriwat N;Jia T;Carroll PJ;Dreher SD;Tudge MT;Yin H;Robinson JR;Schelter EJ;Walsh PJ
通讯作者：
Walsh PJ
影响因子：
2.8
作者：
Miloserdov, Fedor M.;McMullin, Claire L.;Grushin, Vladimir V.
通讯作者：
Grushin, Vladimir V.
影响因子：
2.8
作者：
Cucullu, ME;Nolan, SP;Grubbs, RH
通讯作者：
Grubbs, RH
影响因子：
15
作者：
Gatard, S;Çelenligil-Çetin, R;Ozerov, OV
通讯作者：
Ozerov, OV
影响因子：
15
作者：
Grushin, VV;Marshall, WJ
通讯作者：
Marshall, WJ