10.1021/ic061344e.s002
Celedonio M. Alvarez
Celedonio M.
Alvarez
M. Angeles Alvarez
M. Angeles
Alvarez
María Alonso
María
Alonso
M. Esther García
M. Esther
García
M. Teresa Rueda
M. Teresa
Rueda
Miguel A. Ruiz
Miguel A.
Ruiz
Patrick Herson
Patrick
Herson
Trapping of Hemiquinone Radicals at Mo and P Sites by
Phosphide-Bridged Dimolybdenum Species: Chemistry of Complexes
[Mo<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(OC<sub>6</sub>H<sub>4</sub>OH)(μ-PR<sub>2</sub>)(CO)<sub>4</sub>] and
[Mo<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>{μ-PR(OC<sub>6</sub>H<sub>4</sub>OH)}(CO)<sub>4</sub>]<sup>-</sup> (R = Cy, Ph)
American Chemical Society
2006
OH
DBU
ER
cyclohexyl anion experiences
OC 4H OPh
complex
Mo 2Cp
Mo 2Cp displays
2006-11-13 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Trapping_of_Hemiquinone_Radicals_at_Mo_and_P_Sites_by_Phosphide_Bridged_Dimolybdenum_Species_Chemistry_of_Complexes_Mo_sub_2_sub_sup_5_sup_C_sub_5_sub_H_sub_5_sub_sub_2_sub_OC_sub_6_sub_H_sub_4_sub_OH_PR_sub_2_sub_CO_sub_4_sub_and_Mo_sub_2_sub_sup_5_sup_C/3048487
The phosphide-bridged dimolybdenum complexes (H-DBU)[Mo<sub>2</sub>Cp<sub>2</sub>(μ-PR<sub>2</sub>)(CO)<sub>4</sub>] (R= Cy, Ph; DBU = 1,8-diazabicyclo[5.4.0.]undec-7-ene) react with <i>p</i>-benzoquinone to give the hemiquinone complexes [Mo<sub>2</sub>Cp<sub>2</sub>(OC<sub>6</sub>H<sub>4</sub>OH)(μ-PR<sub>2</sub>)(CO)<sub>4</sub>]. The latter experience facile homolytic cleavage of the corresponding Mo−O bonds and react
readily at room temperature with HSPh or S<sub>2</sub>Ph<sub>2</sub> to give the thiolate complexes [Mo<sub>2</sub>Cp<sub>2</sub>(μ-PCy<sub>2</sub>)(μ-SPh)(CO)<sub>4</sub>] or
[Mo<sub>2</sub>Cp<sub>2</sub>(μ-PR<sub>2</sub>)(μ-SPh)(CO)<sub>2</sub>]. In contrast, PRH-bridged substrates experience overall insertion of quinone into the
P−H bond to give the anionic compounds (H-DBU)[Mo<sub>2</sub>Cp<sub>2</sub>{μ-PR(OC<sub>6</sub>H<sub>4</sub>OH)}(CO)<sub>4</sub>], which upon acidification yield
the corresponding neutral hydrides. The cyclohexyl anion experiences rapid nucleophilic displacement of the
hemiquinone group by different anions ER<sup>-</sup> (ER = OH, OMe, OC<sub>4</sub>H<sub>5</sub>, OPh, SPh) to give novel anionic compounds
(H-DBU)[Mo<sub>2</sub>Cp<sub>2</sub>{μ-PCy(ER)}(CO)<sub>4</sub>], which upon acidification yield the corresponding neutral hydrides. The structure
of four of these hydride complexes [PPh(OC<sub>6</sub>H<sub>4</sub>OH), PCy(OH), PCy(OMe), and PCy(OPh) bridges] was determined
by X-ray diffraction methods and confirmed the presence of cis and trans isomers in several of these complexes.
In addition, it was found that the hydroxyphosphide anion [Mo<sub>2</sub>Cp<sub>2</sub>{μ-PCy(OH)}(CO)<sub>4</sub>]<sup>-</sup> displays in solution an
unprecedented tautomeric equilibrium with its hydride-oxophosphinidene isomer [Mo<sub>2</sub>Cp<sub>2</sub>(μ-H){μ-PCy(O)}(CO)<sub>4</sub>]<sup>-</sup>.