10.1021/ja054941t.s003
María Alonso
María
Alonso
M. Angeles Alvarez
M. Angeles
Alvarez
M. Esther García
M. Esther
García
Miguel A. Ruiz
Miguel A.
Ruiz
Hayrullo Hamidov
Hayrullo
Hamidov
John C. Jeffery
John C.
Jeffery
Oxidation Reactions of the Phosphinidene Oxide Ligand
American Chemical Society
2005
Mo 2 Cp 2
thiooxophosphorane complexes
S 8
Bu
Phosphinidene Oxide Ligand
BF 4
multisite activity
phosphinous acid
OH
Oxidation Reactions
DBU
P atoms
OP
SP
oxidizing agents
thiooxophosphorane anion
2 CO 2
EP
novel organophosphorus ligands
bond
phosphinidene oxide
MoCp
O positions
novel dioxophosphorane
sulfur atoms
FeCp 2
P site
2005-11-02 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Oxidation_Reactions_of_the_Phosphinidene_Oxide_Ligand/3259564
The (H-DBU)<sup>+</sup> salt of the anionic phosphinidene oxide complex [MoCp(CO)<sub>2</sub>{P(O)R*}]<sup>-</sup> (<b>1</b>) (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene; R* = 2,4,6-C<sub>6</sub>H<sub>2</sub><i><sup>t</sup></i><sup></sup>Bu<sub>3</sub>) reacts with different oxidizing agents, displaying a multisite activity located at the Mo and P atoms or at the MoP bond. Thus, reaction of <b>1</b> with [FeCp<sub>2</sub>]BF<sub>4</sub> gives the dimer [Mo<sub>2</sub>Cp<sub>2</sub>(CO)<sub>4</sub>{P(O)R*}<sub>2</sub>], and reaction with bromine gives the phosphinous acid complex [MoBrCp{P(OH)(CH<sub>2</sub>CMe<sub>2</sub>C<sub>6</sub>H<sub>2</sub><i><sup>t</sup></i><sup></sup>Bu<sub>2</sub>}(CO)<sub>2</sub>], the latter arising from an unprecedented C−H bond addition to the oxide PO moiety. In contrast, reaction of <b>1</b> with <i>p</i>-benzoquinone occurs at the P site to give the <i>P</i>,<i>O</i>-bound phosphonite complex [MoCp{κ<sup>2</sup>-OP(OC<sub>6</sub>H<sub>4</sub>OH)R*}(CO)<sub>2</sub>]. Finally, oxygen or sulfur atoms are added to the MoP bond by reaction of <b>1</b> with Me<sub>2</sub>CO<sub>2</sub> and S<sub>8</sub> to give the novel dioxophosphorane or thiooxophosphorane complexes [MoCp(CO)<sub>2</sub>{κ<sup>2</sup>-EP(O)R*}]<sup>-</sup> (E = O, S). The thiooxophosphorane anion is a good nucleophile and is methylated at either the S or O positions depending on the electrophile used (MeI or (Me<sub>3</sub>O)BF<sub>4</sub>) to give the isomers [MoCp{κ<sup>2</sup>-(MeS)P(O)R*}(CO)<sub>2</sub>] and [MoCp{κ<sup>2</sup>-SP(OMe)R*}(CO)<sub>2</sub>], both having novel organophosphorus ligands.