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Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes.

ABSTRACT: Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes*P=C(CH(3))-(C(4)H(2)P(Ph))-R 5?a-c (Mes*=2,4,6-tBu(3)Ph; R=2-pyridyl (a), 2-thienyl (b), phenyl (c)) have been prepared from octa-1,7-diyne-substituted phosphaalkenes by utilizing the Fagan-Nugent route. The presence of two differently hybridized phosphorus centers (?(2) ,?(3) and ?(3) ,?(3)) in 5 offers the possibility to selectively tune the HOMO-LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5?a-c by sulfur proceeds exclusively at the ?(3) ,?(3) -phosphorus atom, thus giving rise to the corresponding thioxophospholes 6?a-c. Similarly, 5?a is selectively coordinated by AuCl at the ?(3),?(3) -phosphorus atom. Subsequent second AuCl coordination at the ?(2),?(3) -phosphorus heteroatom results in a dimetallic species that is characterized by a gold-gold interaction that provokes a change in ? conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO-LUMO gap relative to reference phosphole-containing ? systems that lack a P=C substituent.

SUBMITTER: Oberg E

PROVIDER: S-EPMC4506554 | biostudies-literature | 2014 Jul

REPOSITORIES: biostudies-literature

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Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes.

Öberg Elisabet E Orthaber Andreas A Lescop Christophe C Réau Régis R Hissler Muriel M Ott Sascha S

Chemistry (Weinheim an der Bergstrasse, Germany) 20140530 27

Phosphole-substituted phosphaalkenes (PPAs) of the general formula Mes*P=C(CH(3))-(C(4)H(2)P(Ph))-R 5 a-c (Mes*=2,4,6-tBu(3)Ph; R=2-pyridyl (a), 2-thienyl (b), phenyl (c)) have been prepared from octa-1,7-diyne-substituted phosphaalkenes by utilizing the Fagan-Nugent route. The presence of two differently hybridized phosphorus centers (σ(2) ,λ(3) and σ(3) ,λ(3)) in 5 offers the possibility to selectively tune the HOMO-LUMO gap of the compounds by utilizing the different reactivity of the two pho ...[more]

PMID: 24890504

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Project description:BACKGROUND:Several mechanistic models aim to explain the diversification of the multitude of endemic species on Madagascar. The island's biogeographic history probably offered numerous opportunities for secondary contact and subsequent hybridization. Existing diversification models do not consider a possible role of these processes. One key question for a better understanding of their potential importance is how they are influenced by different environmental settings. Here, we characterized a contact zone between two species of mouse lemurs, Microcebus griseorufus and M. murinus, in dry spiny bush and mesic gallery forest that border each other sharply without intermediate habitats between them. We performed population genetic analyses based on mtDNA sequences and nine nuclear microsatellites and compared the results to a known hybrid zone of the same species in a nearby wide gradient from dry spiny bush over transitional forest to humid littoral forest. RESULTS:In the spiny-gallery system, Microcebus griseorufus is restricted to the spiny bush; Microcebus murinus occurs in gallery forest and locally invades the dryer habitat of its congener. We found evidence for bidirectional introgressive hybridization, which is closely linked to increased spatial overlap within the spiny bush. Within 159 individuals, we observed 18 hybrids with mitochondrial haplotypes of both species. Analyses of simulated microsatellite data indicate that we identified hybrids with great accuracy and that we probably underestimated their true number. We discuss short-term climatic fluctuations as potential trigger for the dynamic of invasion and subsequent hybridization. In the gradient hybrid zone in turn, long-term aridification could have favored unidirectional nuclear introgression from Microcebus griseorufus into M. murinus in transitional forest. CONCLUSIONS:Madagascar's southeastern transitional zone harbors two very different hybrid zones of mouse lemurs in different environmental settings. This sheds light on the multitude of opportunities for the formation of hybrid zones and indicates an important influence of environmental factors on secondary contact and hybridization. Our findings suggest that hybridization could enhance the adaptability of mouse lemurs without necessarily leading to a loss of distinctiveness. They point to a potential role of hybridization in Madagascar's diversification history that requires further investigation.

Dataset Information

Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes.

Publications

Phosphorus centers of different hybridization in phosphaalkene-substituted phospholes.

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