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Title: Multiple metal additions to C{sub 60}. An ab initio study of [M(PH{sub 3}){sub 2}]{sub n}C{sub 60} (M = Pt and Pd; n = 1, 2, and 6)

Abstract

A full geometry optimization at the HF level has been carried out for the fullerene platinum complexes [Pt(PH{sub 3}){sub 2}]{sub n}C{sub 60}, n = 1, 2, and 6, and for the hexasubstituted palladium derivative [Pd(PH{sub 3}){sub 2}]{sub 6}C{sub 60}. The computed geometries are in good agreement with those determined by X-ray diffraction. When there is just one platinum bound to C{sub 60}, the binding energy is found to be 11.7 kcal/mol higher than the calculated Pt-ethylene binding energy. The interaction between the metal and C{sub 60} is basically local. As a matter of fact, the dissociation energy of the first metal group in [Pt(PH{sub 3}){sub 2}]{sub 2}C{sub 60} is just 2.7 kcal/mol lower than the dissociation energy of the Pt(PH{sub 3}){sub 2} fragment in the monosubstituted derivative. The total binding energy of the six platinum groups in [Pt(PH{sub 3}){sub 2}]{sub 6}C{sub 60} has been computed to be 30.4 kcal/mol (5.1 kcal/mol per group). An important charge transfer from the metal group to the C{sub 60} core has been detected, about 0.5e for the monosubstituted derivative and 2.2e for the hexasubstituted platinum complex. The Pd(PH{sub 3}){sub 2} group has been determined to be more labile than the corresponding platinum group. Themore » M-C{sub 60} bond strength is noticeably weakened if the complex is reduced. Hence, the loss of C{sub 60}{sup -} from [Pt(PH{sub 3}){sub 2}]{sub 2}(C{sub 60}){sup -} is 12.5 kcal/mol more favorable than the loss of C{sub 60} from its neutral partner. 48 refs., 6 figs., 8 tabs.« less

Authors:
; ;  [1]
  1. Universitat Rovira i Virgili, Tarragona (Spain)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
45004
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry
Additional Journal Information:
Journal Volume: 99; Journal Issue: 16; Other Information: PBD: 20 Apr 1995
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 40 CHEMISTRY; 99 MATHEMATICS, COMPUTERS, INFORMATION SCIENCE, MANAGEMENT, LAW, MISCELLANEOUS; PLATINUM COMPLEXES; BINDING ENERGY; DISSOCIATION ENERGY; PALLADIUM COMPLEXES; THEORETICAL DATA; FULLERENES; MOLECULAR ORBITAL METHOD; CHARGE TRANSPORT; BOND ANGLE; BOND LENGTHS; ELECTRONIC STRUCTURE; MOLECULAR STRUCTURE; AFFINITY

Citation Formats

Bo, C, Costas, M, and Poblet, J M. Multiple metal additions to C{sub 60}. An ab initio study of [M(PH{sub 3}){sub 2}]{sub n}C{sub 60} (M = Pt and Pd; n = 1, 2, and 6). United States: N. p., 1995. Web. doi:10.1021/j100016a028.
Bo, C, Costas, M, & Poblet, J M. Multiple metal additions to C{sub 60}. An ab initio study of [M(PH{sub 3}){sub 2}]{sub n}C{sub 60} (M = Pt and Pd; n = 1, 2, and 6). United States. https://doi.org/10.1021/j100016a028
Bo, C, Costas, M, and Poblet, J M. Thu . "Multiple metal additions to C{sub 60}. An ab initio study of [M(PH{sub 3}){sub 2}]{sub n}C{sub 60} (M = Pt and Pd; n = 1, 2, and 6)". United States. https://doi.org/10.1021/j100016a028.
@article{osti_45004,
title = {Multiple metal additions to C{sub 60}. An ab initio study of [M(PH{sub 3}){sub 2}]{sub n}C{sub 60} (M = Pt and Pd; n = 1, 2, and 6)},
author = {Bo, C and Costas, M and Poblet, J M},
abstractNote = {A full geometry optimization at the HF level has been carried out for the fullerene platinum complexes [Pt(PH{sub 3}){sub 2}]{sub n}C{sub 60}, n = 1, 2, and 6, and for the hexasubstituted palladium derivative [Pd(PH{sub 3}){sub 2}]{sub 6}C{sub 60}. The computed geometries are in good agreement with those determined by X-ray diffraction. When there is just one platinum bound to C{sub 60}, the binding energy is found to be 11.7 kcal/mol higher than the calculated Pt-ethylene binding energy. The interaction between the metal and C{sub 60} is basically local. As a matter of fact, the dissociation energy of the first metal group in [Pt(PH{sub 3}){sub 2}]{sub 2}C{sub 60} is just 2.7 kcal/mol lower than the dissociation energy of the Pt(PH{sub 3}){sub 2} fragment in the monosubstituted derivative. The total binding energy of the six platinum groups in [Pt(PH{sub 3}){sub 2}]{sub 6}C{sub 60} has been computed to be 30.4 kcal/mol (5.1 kcal/mol per group). An important charge transfer from the metal group to the C{sub 60} core has been detected, about 0.5e for the monosubstituted derivative and 2.2e for the hexasubstituted platinum complex. The Pd(PH{sub 3}){sub 2} group has been determined to be more labile than the corresponding platinum group. The M-C{sub 60} bond strength is noticeably weakened if the complex is reduced. Hence, the loss of C{sub 60}{sup -} from [Pt(PH{sub 3}){sub 2}]{sub 2}(C{sub 60}){sup -} is 12.5 kcal/mol more favorable than the loss of C{sub 60} from its neutral partner. 48 refs., 6 figs., 8 tabs.},
doi = {10.1021/j100016a028},
url = {https://www.osti.gov/biblio/45004}, journal = {Journal of Physical Chemistry},
number = 16,
volume = 99,
place = {United States},
year = {1995},
month = {4}
}