An Amplified Ylidic “Half-Parent” Iminosilane LSiNH

The reaction of LSiBr­(NH₂) (<b>4</b>) (L = CH­[(CCH₂)­CMe­(NAr)₂]; Ar = 2,6-<i>i</i>Pr₂C₆H₃) with lithium bis­(trimethylsilyl)­amide in the presence of pyridine or 4-dimethylaminopyridine (DMAP) resulted in the activation of the α C–H bond of pyridine or DMAP, affording the products LSi­(dmap)­NH₂ (<b>6</b>) and LSi­(pyridine)­NH₂ (<b>7a</b>), respectively. Remarkably, this metal-free aromatic C–H activation occurs at room temperature. The emerging aminosilanes were isolated and fully characterized. Isotope labeling experiments and detailed DFT calculations, elucidating the reaction mechanism, were performed and provide compelling evidence of the formation of the “half-parent” iminosilane <b>1</b>, LSiNH, which facilitates this transformation due to its amplified ylidic character by the chelate ligand L. Furthermore, the elusive iminosilane <b>1</b> could be trapped by benzophenone and trimethylsilylazide affording the corresponding products, <b>8</b> and <b>9,</b> respectively, thereby confirming its formation as a key intermediate

A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)

The simplest parent phosphinidene, :PH (<b>1</b>), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solution has now been accomplished by taking advantage of the facile homolytic bond cleavage of the fragile SiP bond of the first zwitterionic phosphasilene LSi=PH (<b>8</b>) (L = CH­[(CCH₂)­CMe­(NAr)₂]; Ar = 2,6-^<i>i</i>Pr₂C₆H₃). The latter bears two highly localized lone pairs on the phosphorus atom due to the LSiPH ↔ LSi⁺–PH^– resonance structures. Strikingly, the dissociation of <b>8</b> in hydrocarbon solutions occurs even at room temperature, affording the N-heterocyclic silylene LSi: (<b>9</b>) and <b>1</b>, which leads to oligomeric [PH]_<i>n</i> clusters in the absence of a trapping agent. However, in the presence of an N-heterocyclic carbene as an unsaturated organic substrate, the fragile phosphasilene <b>8</b> acts as a :PH transfer reagent, resulting in the formation of silylene <b>9</b> and phosphaalkene <b>11</b> bearing a terminal PH moiety

A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)

The simplest parent phosphinidene, :PH (<b>1</b>), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solution has now been accomplished by taking advantage of the facile homolytic bond cleavage of the fragile SiP bond of the first zwitterionic phosphasilene LSi=PH (<b>8</b>) (L = CH­[(CCH₂)­CMe­(NAr)₂]; Ar = 2,6-^<i>i</i>Pr₂C₆H₃). The latter bears two highly localized lone pairs on the phosphorus atom due to the LSiPH ↔ LSi⁺–PH^– resonance structures. Strikingly, the dissociation of <b>8</b> in hydrocarbon solutions occurs even at room temperature, affording the N-heterocyclic silylene LSi: (<b>9</b>) and <b>1</b>, which leads to oligomeric [PH]_<i>n</i> clusters in the absence of a trapping agent. However, in the presence of an N-heterocyclic carbene as an unsaturated organic substrate, the fragile phosphasilene <b>8</b> acts as a :PH transfer reagent, resulting in the formation of silylene <b>9</b> and phosphaalkene <b>11</b> bearing a terminal PH moiety

A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)

The simplest parent phosphinidene, :PH (<b>1</b>), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solution has now been accomplished by taking advantage of the facile homolytic bond cleavage of the fragile SiP bond of the first zwitterionic phosphasilene LSi=PH (<b>8</b>) (L = CH­[(CCH₂)­CMe­(NAr)₂]; Ar = 2,6-^<i>i</i>Pr₂C₆H₃). The latter bears two highly localized lone pairs on the phosphorus atom due to the LSiPH ↔ LSi⁺–PH^– resonance structures. Strikingly, the dissociation of <b>8</b> in hydrocarbon solutions occurs even at room temperature, affording the N-heterocyclic silylene LSi: (<b>9</b>) and <b>1</b>, which leads to oligomeric [PH]_<i>n</i> clusters in the absence of a trapping agent. However, in the presence of an N-heterocyclic carbene as an unsaturated organic substrate, the fragile phosphasilene <b>8</b> acts as a :PH transfer reagent, resulting in the formation of silylene <b>9</b> and phosphaalkene <b>11</b> bearing a terminal PH moiety

A Fragile Zwitterionic Phosphasilene as a Transfer Agent of the Elusive Parent Phosphinidene (:PH)

The simplest parent phosphinidene, :PH (<b>1</b>), has been observed only in the gas phase or low temperature matrices and has escaped rigorous characterization because of its high reactivity. Its liberation and transfer to an unsaturated organic molecule in solution has now been accomplished by taking advantage of the facile homolytic bond cleavage of the fragile SiP bond of the first zwitterionic phosphasilene LSi=PH (<b>8</b>) (L = CH­[(CCH₂)­CMe­(NAr)₂]; Ar = 2,6-^<i>i</i>Pr₂C₆H₃). The latter bears two highly localized lone pairs on the phosphorus atom due to the LSiPH ↔ LSi⁺–PH^– resonance structures. Strikingly, the dissociation of <b>8</b> in hydrocarbon solutions occurs even at room temperature, affording the N-heterocyclic silylene LSi: (<b>9</b>) and <b>1</b>, which leads to oligomeric [PH]_<i>n</i> clusters in the absence of a trapping agent. However, in the presence of an N-heterocyclic carbene as an unsaturated organic substrate, the fragile phosphasilene <b>8</b> acts as a :PH transfer reagent, resulting in the formation of silylene <b>9</b> and phosphaalkene <b>11</b> bearing a terminal PH moiety

Distribution of Medication Possession Ratio.

<p>Distribution of Medication Possession Ratio.</p

Distribution of Medication Possession Ratio.

<p>Distribution of Medication Possession Ratio.</p

Sensitivity analysis (S1): Proportion of profiles of compliant patients for three different thresholds of MPR.

<p>Sensitivity analysis (S1): Proportion of profiles of compliant patients for three different thresholds of MPR.</p

Sensitivity analysis (S2): Proportion of profiles of persistent patients for three different definitions for the tolerable gap in medication profiles.

<p>Sensitivity analysis (S2): Proportion of profiles of persistent patients for three different definitions for the tolerable gap in medication profiles.</p

Cohort definition and observation period of the study.

<p>Cohort definition and observation period of the study.</p