Publication: Estudio computacional de la energía de tensión de anillos de tres miembros
Authors
Rey Planells, Alicia
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Escuela Internacional de Doctorado
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Espinosa Ferao, Arturo
Publisher
Universidad de Murcia
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DOI
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info:eu-repo/semantics/doctoralThesis
Description
Abstract
En la presente Tesis Doctoral se cubre la brecha existente en la evaluación
sistemática de valores de RSE de referencia para una amplia gama de anillos de tres
miembros, así como el análisis exhaustivo de los factores que afectan a los mismos. El
conjunto de anillos estudiados incluye las más importantes familias de heterociclos de
tres miembros cabezas de serie (no sustituidos) tanto saturados (CH2)2X como
insaturados (CH)2X, donde X es un elemento (“El”) del grupo 13-16 con su covalencia
típica completada con enlaces con H (X = ElHn, n = 1, 2, 1 y 0 para elementos El de los
grupos 13, 14, 15 y 16, respectivamente). De la misma manera, se extiende el estudio a
anillos con dos o tres heteroátomos idénticos, (CH2)X2 y X3, conjuntamente con
tetreliranos más pesados (SiH2)X2 y (GeH2)X2. Debido al emergente interés del
oxafosfirano y sus derivados en la construcción de nuevos materiales poliméricos
fosforados mediante ROP, se lleva a cabo un análisis más específico tanto del
compuesto cabeza de serie como de oxafosfiranos diferentemente P- y C-sustituidos o
funcionalizados. Por otro lado, se realiza una prospección de la PES ( de sus siglas en
inglés Potential Energy Surface) de los isómeros cabeza de serie (cíclicos y acíclicos)
CHPnO (Pn, N, P) y otros derivados sustituidos teniendo la oxazirina y en oxafosfireno
como moléculas centrales a través de las cuales se puede llegar al resto de isómeros
mediante la escisión de sus tres enlaces endocíclicos. También se presentan la PES de
los derivados aniónicos COPn-. Por último, se plantea la interesante cuestión de si es
posible determinar cuantitativamente la contribución de cada enlace y/o átomo del
anillo al RSE total, para poder acceder a estimaciones mediante una metodología
aditiva.
The present PhD Thesis significantly fills the existing gap in the systematic evaluation of benchmark RSE values for a wide range of three-membered rings, as well as a comprehensive analysis of the factors affecting them. The set of rings studied includes the most important three-membered families of parent (unsubstituted) saturated (CH2)2X and unsaturated (CH)2X heterocycles, where X is an element ("El") of the group 13-16 with its typical covalency completed with H-bonds (X = ElHn, n = 1, 2, 1 and 0 for El elements of groups 13, 14, 15 and 16, respectively). In the same way, the study is extended to rings with two or three identical heteroatoms, (CH2)X2 and X3, together with heavier tetreliranes (SiH2)X2 and (GeH2)X2 (Scheme 3). Due to the emerging interest of oxaphosphirane and its derivatives in the construction of new phosphorous polymeric materials by ROP, a more specific analysis of both the parent oxaphosphirane and differently P- and C-substituted or functionalised derivatives is carried out. On the other hand, the PES (Potential Energy Surface) of parent CHPnO (Pn, N, P) and other substituted derivatives is explored, having oxazirine and oxaphosphirene as central molecules through which the rest of isomers can be reached by cleavage of their three endocyclic bonds. The PES of the anionic COPnderivatives are also presented. Finally, the interesting question arises as to whether it is possible to quantitatively determine the contribution of each ring bond and/or atom to the total RSE, so that fast estimates can be made using an additive methodology.
The present PhD Thesis significantly fills the existing gap in the systematic evaluation of benchmark RSE values for a wide range of three-membered rings, as well as a comprehensive analysis of the factors affecting them. The set of rings studied includes the most important three-membered families of parent (unsubstituted) saturated (CH2)2X and unsaturated (CH)2X heterocycles, where X is an element ("El") of the group 13-16 with its typical covalency completed with H-bonds (X = ElHn, n = 1, 2, 1 and 0 for El elements of groups 13, 14, 15 and 16, respectively). In the same way, the study is extended to rings with two or three identical heteroatoms, (CH2)X2 and X3, together with heavier tetreliranes (SiH2)X2 and (GeH2)X2 (Scheme 3). Due to the emerging interest of oxaphosphirane and its derivatives in the construction of new phosphorous polymeric materials by ROP, a more specific analysis of both the parent oxaphosphirane and differently P- and C-substituted or functionalised derivatives is carried out. On the other hand, the PES (Potential Energy Surface) of parent CHPnO (Pn, N, P) and other substituted derivatives is explored, having oxazirine and oxaphosphirene as central molecules through which the rest of isomers can be reached by cleavage of their three endocyclic bonds. The PES of the anionic COPnderivatives are also presented. Finally, the interesting question arises as to whether it is possible to quantitatively determine the contribution of each ring bond and/or atom to the total RSE, so that fast estimates can be made using an additive methodology.
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