Abstract
White phosphorus (P4) reacts with three-coordinate molybdenum(III) trisamides or molybdaziridine hydride complexes to produce either bridging or terminal phosphide (P3-) species, depending upon the ancillary ligand steric demands. Thermochemical measurements have been made that place the Mo=P triple bond dissociation enthalpy at 92.2 kcal·mol-1. Thermochemical measurements together with computational analysis rule out simple P-atom abstraction from P4 as a step in the phosphorus activation mechanism. Kinetic measurements made by the stopped-flow method show that the reaction between the monomeric molybdenum complexes and P4 is first-order both in metal complex and in P 4. cyclo-P3 complexes can be obtained when ancillary ligand steric demands are small, but kinetic measurements rule them out as monometallic intermediates in the P4 activation mechanism. Also studied by calorimetric, kinetic, and in one case variable-temperature NMR methods is the process of μ-phosphide bridge formation. Post-rate-determining steps of the P4 activation process were examined in a search for minima on the reaction's potential energy surface, leading to the proposal of two plausible, parallel, bimetallic reaction channels.
| Original language | English |
|---|---|
| Pages (from-to) | 15191-15200 |
| Number of pages | 10 |
| Journal | Journal of the American Chemical Society |
| Volume | 127 |
| Issue number | 43 |
| DOIs | |
| State | Published - Nov 2 2005 |
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ASJC Scopus subject areas
- Chemistry(all)
Cite this
Mechanism of white phosphorus activation by three-coordinate molybdenum(III) complexes : A thermochemical, kinetic, and quantum chemical investigation. / Stephens, Frances H.; Johnson, Marc J A; Cummins, Christopher C.; Kryatova, Olga P.; Kryatov, Sergey V.; Rybak-Akimova, Elena V.; McDonough, J. Eric; Hoff, Carl.
In: Journal of the American Chemical Society, Vol. 127, No. 43, 02.11.2005, p. 15191-15200.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Mechanism of white phosphorus activation by three-coordinate molybdenum(III) complexes
T2 - A thermochemical, kinetic, and quantum chemical investigation
AU - Stephens, Frances H.
AU - Johnson, Marc J A
AU - Cummins, Christopher C.
AU - Kryatova, Olga P.
AU - Kryatov, Sergey V.
AU - Rybak-Akimova, Elena V.
AU - McDonough, J. Eric
AU - Hoff, Carl
PY - 2005/11/2
Y1 - 2005/11/2
N2 - White phosphorus (P4) reacts with three-coordinate molybdenum(III) trisamides or molybdaziridine hydride complexes to produce either bridging or terminal phosphide (P3-) species, depending upon the ancillary ligand steric demands. Thermochemical measurements have been made that place the Mo=P triple bond dissociation enthalpy at 92.2 kcal·mol-1. Thermochemical measurements together with computational analysis rule out simple P-atom abstraction from P4 as a step in the phosphorus activation mechanism. Kinetic measurements made by the stopped-flow method show that the reaction between the monomeric molybdenum complexes and P4 is first-order both in metal complex and in P 4. cyclo-P3 complexes can be obtained when ancillary ligand steric demands are small, but kinetic measurements rule them out as monometallic intermediates in the P4 activation mechanism. Also studied by calorimetric, kinetic, and in one case variable-temperature NMR methods is the process of μ-phosphide bridge formation. Post-rate-determining steps of the P4 activation process were examined in a search for minima on the reaction's potential energy surface, leading to the proposal of two plausible, parallel, bimetallic reaction channels.
AB - White phosphorus (P4) reacts with three-coordinate molybdenum(III) trisamides or molybdaziridine hydride complexes to produce either bridging or terminal phosphide (P3-) species, depending upon the ancillary ligand steric demands. Thermochemical measurements have been made that place the Mo=P triple bond dissociation enthalpy at 92.2 kcal·mol-1. Thermochemical measurements together with computational analysis rule out simple P-atom abstraction from P4 as a step in the phosphorus activation mechanism. Kinetic measurements made by the stopped-flow method show that the reaction between the monomeric molybdenum complexes and P4 is first-order both in metal complex and in P 4. cyclo-P3 complexes can be obtained when ancillary ligand steric demands are small, but kinetic measurements rule them out as monometallic intermediates in the P4 activation mechanism. Also studied by calorimetric, kinetic, and in one case variable-temperature NMR methods is the process of μ-phosphide bridge formation. Post-rate-determining steps of the P4 activation process were examined in a search for minima on the reaction's potential energy surface, leading to the proposal of two plausible, parallel, bimetallic reaction channels.
UR - http://www.scopus.com/inward/record.url?scp=27544460115&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=27544460115&partnerID=8YFLogxK
U2 - 10.1021/ja054253+
DO - 10.1021/ja054253+
M3 - Article
C2 - 16248661
AN - SCOPUS:27544460115
VL - 127
SP - 15191
EP - 15200
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 43
ER -