2019
DOI: 10.1002/ange.201901470
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Interconversion of Phosphinyl Radical and Phosphinidene Complexes by Proton Coupled Electron Transfer

Abstract: The isolable complex [Os(PHMes*)H(PNP)] (Mes* = 2,4,6-t Bu 3 C 6 H 3 ;P NP = N{CHCHP t Bu 2 } 2 )e xhibits high phosphinyl radical character.T his compound offers access to the phosphinidene complex [Os(PMes*)H(PNP)] by PÀHp roton coupled electron transfer (PCET). The PÀH bond dissociation energy (BDE) was determined by isothermal titration calorimetry and supporting DFT computations.T he phosphinidene product exhibits electrophilic reactivity as demonstrated by intramolecular C À Ha ctivation. : osmium ·p hos… Show more

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Cited by 10 publications
(6 citation statements)
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“…26,58,59,60 This observation is in line with predominantly diphosphenediide-centered oxidation of 2 and an unsymmetric spin density distribution of radical cation 3. 64 DFT calculations confirm this picture and locate the spin density of 3 mainly on the P2 fragment (Figure 2C) as a result of depopulation of the *(P2) HOMO of parent 2. Accordingly, the P-P bond order increases upon oxidation, as reflected by the Wiberg bond orders and the QTAIM delocalization indices (WBI; 2: 1.86, 3: 2.09, and DI(P,P); 2: 1.81, 3: 1.95; Figure S81-S82).…”
Section: Stepwise Oxidation Of the P2 2bridgementioning
confidence: 53%
“…26,58,59,60 This observation is in line with predominantly diphosphenediide-centered oxidation of 2 and an unsymmetric spin density distribution of radical cation 3. 64 DFT calculations confirm this picture and locate the spin density of 3 mainly on the P2 fragment (Figure 2C) as a result of depopulation of the *(P2) HOMO of parent 2. Accordingly, the P-P bond order increases upon oxidation, as reflected by the Wiberg bond orders and the QTAIM delocalization indices (WBI; 2: 1.86, 3: 2.09, and DI(P,P); 2: 1.81, 3: 1.95; Figure S81-S82).…”
Section: Stepwise Oxidation Of the P2 2bridgementioning
confidence: 53%
“…Theslightly exothermic (D r H o HAT = À3.83 AE 0.05 kJ mol À1 ) and endergonic (D r G o HAT =+0.0162 AE 0.087 kJ mol À1 )r eaction allowed for estimating BDE IrOÀH THF (5) = 350 AE 2kJmol À1 and BDFE IrOÀH THF (5) = 325 AE 6kJmol À1 , [15] which is slightly lower compared with arecently reported cobalt(III) hydroxo complex, [Co(OH){PhB(tBuIm) 3 [21] Minor changes in vibrational and electronic entropies can be expected for 5d metal complexes with energetically well-separated electronic ground states,such as 5 and 8 (Figure 3a,b). [22] Explicitly correlated coupled-cluster computations including spin-orbit coupling and solvent effects give an IrO À HB DE of 342 kJ mol À1 ,i ne xcellent agreement with experiment.…”
Section: Zuschriftenmentioning
confidence: 88%
“…Theslightly exothermic (D r H o HAT = À3.83 AE 0.05 kJ mol À1 ) and endergonic (D r G o HAT =+0.0162 AE 0.087 kJ mol À1 )r eaction allowed for estimating BDE IrOÀH THF (5) = 350 AE 2kJmol À1 and BDFE IrOÀH THF (5) = 325 AE 6kJmol À1 , [15] [21] Minor changes in vibrational and electronic entropies can be expected for 5d metal complexes with energetically well-separated electronic ground states,such as 5 and 8 (Figure 3a,b). [22] Explicitly correlated coupled-cluster computations including spin-orbit coupling and solvent effects give an IrO À HB DE of 342 kJ mol À1 ,i ne xcellent agreement with experiment.…”
Section: Zuschriftenmentioning
confidence: 99%