AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX
The four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Academy of Sciences of Moldova, Institute of Chemistry
2011-12-01
|
| Series: | Chemistry Journal of Moldova: General, Industrial and Ecological Chemistry |
| Subjects: | |
| Online Access: | http://www.cjm.asm.md/sites/default/files/article_files/Balan%20018%20.pdf |
| _version_ | 1818821604494278656 |
|---|---|
| author | Iolanta I. Balan Natalia N. Gorinchoy |
| author_facet | Iolanta I. Balan Natalia N. Gorinchoy |
| author_sort | Iolanta I. Balan |
| collection | DOAJ |
| description | The four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of reactants, products, and intermediate complexes of reaction. It is shown that generation of the transient complex [(triphos)RhH(η1:η1-P4)] followed by intramolecular hydrogen atom migration from the metal to one of the phosphorus atoms is the energetically favourable process. Calculations also show that P4 molecule is activated by coordination to the above complex: the metal-bonded P-P edge is broken, and the tetrahedron P4 is opened to form the butterfly geometry. This activation is realized mainly due to the one-orbital back donation of 4d-electron density from the atom of Rh to the unoccupied antibonding triple degenerate t1*-MO of P4. |
| first_indexed | 2024-12-18T23:10:50Z |
| format | Article |
| id | doaj.art-ed5b10cb82e54dadb5ef523e49e8c95c |
| institution | Directory Open Access Journal |
| issn | 1857-1727 2345-1688 |
| language | English |
| last_indexed | 2024-12-18T23:10:50Z |
| publishDate | 2011-12-01 |
| publisher | Academy of Sciences of Moldova, Institute of Chemistry |
| record_format | Article |
| series | Chemistry Journal of Moldova: General, Industrial and Ecological Chemistry |
| spelling | doaj.art-ed5b10cb82e54dadb5ef523e49e8c95c2022-12-21T20:48:22ZengAcademy of Sciences of Moldova, Institute of ChemistryChemistry Journal of Moldova: General, Industrial and Ecological Chemistry1857-17272345-16882011-12-01628490AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEXIolanta I. Balan0Natalia N. Gorinchoy1Institute of Chemistry of Academy of Sciences of MoldovaInstitute of Chemistry of Academy of Sciences of MoldovaThe four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of reactants, products, and intermediate complexes of reaction. It is shown that generation of the transient complex [(triphos)RhH(η1:η1-P4)] followed by intramolecular hydrogen atom migration from the metal to one of the phosphorus atoms is the energetically favourable process. Calculations also show that P4 molecule is activated by coordination to the above complex: the metal-bonded P-P edge is broken, and the tetrahedron P4 is opened to form the butterfly geometry. This activation is realized mainly due to the one-orbital back donation of 4d-electron density from the atom of Rh to the unoccupied antibonding triple degenerate t1*-MO of P4.http://www.cjm.asm.md/sites/default/files/article_files/Balan%20018%20.pdfwhite phosphorustriphosrhodium trihydride complexab initio calculations |
| spellingShingle | Iolanta I. Balan Natalia N. Gorinchoy AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX Chemistry Journal of Moldova: General, Industrial and Ecological Chemistry white phosphorus triphos rhodium trihydride complex ab initio calculations |
| title | AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX |
| title_full | AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX |
| title_fullStr | AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX |
| title_full_unstemmed | AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX |
| title_short | AB INITIO STUDY OF CHEMICAL ACTIVATION AND HYDROGENATION OF WHITE PHOSPHORUS IN REACTION WITH RHODIUM TRIHYDRIDE COMPLEX |
| title_sort | ab initio study of chemical activation and hydrogenation of white phosphorus in reaction with rhodium trihydride complex |
| topic | white phosphorus triphos rhodium trihydride complex ab initio calculations |
| url | http://www.cjm.asm.md/sites/default/files/article_files/Balan%20018%20.pdf |
| work_keys_str_mv | AT iolantaibalan abinitiostudyofchemicalactivationandhydrogenationofwhitephosphorusinreactionwithrhodiumtrihydridecomplex AT nataliangorinchoy abinitiostudyofchemicalactivationandhydrogenationofwhitephosphorusinreactionwithrhodiumtrihydridecomplex |