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1.
Chemistry ; 24(3): 743-749, 2018 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-29106762

RESUMO

The phosphorus-sulfur heterocycles 1,2-thiaphosphetenes and phosphirene sulfides have been prepared, and represent the first structurally characterized derivatives for either class of compound. These strained P-S ring systems are formed by the reaction of a phosphinidene sulfide and alkyne. Using an internal alkyne, only the 3-membered PV , phosphirene sulfide was produced, whereas a terminal alkyne yielded a mixture of phosphirene sulfide and 1,2-thiaphosphetene (PIII ). Detailed computational analysis revealed that for numerous derivatives of alkynes, the corresponding 4-membered rings are always more stable than the 3-membered isomers. The electronic nature of "free" phosphinidene sulfides (R-P=S) is discussed based on computational results.

2.
Chemistry ; 24(3): 672-680, 2018 Jan 12.
Artigo em Inglês | MEDLINE | ID: mdl-29119625

RESUMO

Four-membered rings with a P2 BCh core (Ch=S, Se) have been synthesized by the reaction of phosphinidene chalcogenide (Ar*P=Ch) and phosphaborene (Mes*P=BNR2 ). The mechanistic pathways towards these rings are explained by detailed computational work that confirmed the preference for the formation of P-P, not P-B, bonded systems, which seems counterintuitive given that both phosphorus atoms contain bulky ligands. The reactivity of the newly synthesized heterocycles, as well as that of the known (RPCh)n rings (n=2, 3), was probed by the addition of N-heterocyclic carbenes, which revealed that all investigated compounds can act as sources of low-coordinate phosphorus species.

3.
Inorg Chem ; 56(21): 13500-13509, 2017 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-29027797

RESUMO

The reactivity of 4-membered (RPCh)2 rings (Ch = S, Se) that contain phosphorus in the +3 oxidation state is reported. These compounds undergo ring expansion to (RPCh)3 with the addition of a Lewis base. The 6-membered rings were found to be more stable than the 4-membered precursors, and the mechanism of their formation was investigated experimentally and by density functional theory calculations. The computational work identified two plausible mechanisms involving a phosphinidene chalcogenide intermediate, either as a free species or stabilized by a suitable base. Both the 4- and 6-membered rings were found to react with coinage metals, giving the same products: (RPCh)3 rings bound to the metal center from the phosphorus atom in tripodal fashion.

4.
Inorg Chem ; 56(15): 9111-9119, 2017 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-28737903

RESUMO

The manipulation of white phosphorus (P4) has been a long-standing challenge for chemists. While the holy grail remains at finding a method to catalytically activate and functionalize P4 to yield new organophosphorus compounds, fundamental research lies in developing procedures to control the reactivity of elemental phosphorus. In this work, Lewis acidic transition metal moieties M(CO)5 (M = Cr, Mo, W) and AuCl react with P4 derivatized with a low valent germanium compound. For both M(CO)5 and AuCl, bis-functionalized products can be formed; however the monosubstituted derivatives are found to be more stable, and the decomposition can be monitored by 31P{1H} NMR spectroscopy. The selective reactivity of white phosphorus, once a P-P bond has been activated, is a key step in yielding new organophosphorus compounds.

5.
Angew Chem Int Ed Engl ; 56(22): 6236-6240, 2017 05 22.
Artigo em Inglês | MEDLINE | ID: mdl-28071846

RESUMO

Four-membered rings with a P2 Ch2 core (Ch=S, Se) and phosphorus in the +3 oxidation state have been synthesized. The utility of these rings as a source of monomeric phosphinidene chalcogenides was probed by the addition of an N-heterocyclic carbene, resulting in a base-stabilized phosphinidene sulfide. Similarly, persistence of the phosphinidene selenide in solution was shown through cycloaddition chemistry with 2,3-dimethylbutadiene at elevated temperatures. The observed reactivity was explained by detailed computational work that established the conditions upon which the P2 Ch2 rings can liberate phosphinidene chalcogenides.

6.
Chemistry ; 20(22): 6739-44, 2014 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-24687238

RESUMO

Two unique systems based on low-coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element-phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.

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