title: Thermodynamic, kinetic, and mechanistic study of oxygen atom transfer from mesityl nitrile oxide to phosphines and to a terminal metal phosphido complex.
abstract: The enthalpies of oxygen atom transfer (OAT) from mesityl nitrile oxide (MesCNO) to Me(3)P, Cy(3)P, Ph(3)P, and the complex (Ar[(t)Bu]N)(3)MoP (Ar = 3,5-C(6)H(3)Me(2)) have been measured by solution calorimetry yielding the following P-O bond dissociation enthalpy estimates in toluene solution (±3 kcal mol(-1)): Me(3)PO [138.5], Cy(3)PO [137.6], Ph(3)PO [132.2], (Ar[(t)Bu]N)(3)MoPO [108.9]. The data for (Ar[(t)Bu]N)(3)MoPO yield an estimate of 60.2 kcal mol(-1) for dissociation of PO from (Ar[(t)Bu]N)(3)MoPO. The mechanism of OAT from MesCNO to R(3)P and (Ar[(t)Bu]N)(3)MoP has been investigated by UV-vis and FTIR kinetic studies as well as computationally. Reactivity of R(3)P and (Ar[(t)Bu]N)(3)MoP with MesCNO is proposed to occur by nucleophilic attack by the lone pair of electrons on the phosphine or phosphide to the electrophilic C atom of MesCNO forming an adduct rather than direct attack at the terminal O. This mechanism is supported by computational studies. In addition, reaction of the N-heterocyclic carbene SIPr (SIPr = 1,3-bis(diisopropyl)phenylimidazolin-2-ylidene) with MesCNO results in formation of a stable adduct in which the lone pair of the carbene attacks the C atom of MesCNO. The crystal structure of the blue SIPr·MesCNO adduct is reported, and resembles one of the computed structures for attack of the lone pair of electrons of Me(3)P on the C atom of MesCNO. Furthermore, this adduct in which the electrophilic C atom of MesCNO is blocked by coordination to the NHC does not undergo OAT with R(3)P. However, it does undergo rapid OAT with coordinatively unsaturated metal complexes such as (Ar[(t)Bu]N)(3)V since these proceed by attack of the unblocked terminal O site of the SIPr·MesCNO adduct rather than at the blocked C site. OAT from MesCNO to pyridine, tetrahydrothiophene, and (Ar[(t)Bu]N)(3)MoN was found not to proceed in spite of thermochemical favorability.
authors.affiliation: Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables Florida 33021, United States.
authors.forename: Xiaochen
authors.initials: X
authors.lastname: Cai
authors.forename: Subhojit
authors.initials: S
authors.lastname: Majumdar
authors.forename: George C
authors.initials: GC
authors.lastname: Fortman
authors.forename: Luis Manuel
authors.initials: LM
authors.lastname: Frutos
authors.forename: Manuel
authors.initials: M
authors.lastname: Temprado
authors.forename: Christopher R
authors.initials: CR
authors.lastname: Clough
authors.forename: Christopher C
authors.initials: CC
authors.lastname: Cummins
authors.forename: Meaghan E
authors.initials: ME
authors.lastname: Germain
authors.forename: Taryn
authors.initials: T
authors.lastname: Palluccio
authors.forename: Elena V
authors.initials: EV
authors.lastname: Rybak-Akimova
authors.forename: Burjor
authors.initials: B
authors.lastname: Captain
authors.forename: Carl D
authors.initials: CD
authors.lastname: Hoff
mesh_terms: D002151:Calorimetry; D007700:Kinetics; D009570:Nitriles / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D009570:Nitriles; D010087:Oxides; D010720:Phosphines; D010100:Oxygen