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Title: Late transition metal m-or chemistry and D6 metal complex photoeliminations

Abstract

With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.

Authors:
 [1]
  1. Univ. of Missouri, Columbia, MO (United States)
Publication Date:
Research Org.:
Univ. of Missouri, Columbia, MO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1313940
Report Number(s):
DE-FG02-88ER13880-1
DOE Contract Number:
FG02-88ER13880
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sharp, Paul. Late transition metal m-or chemistry and D6 metal complex photoeliminations. United States: N. p., 2015. Web. doi:10.2172/1313940.
Sharp, Paul. Late transition metal m-or chemistry and D6 metal complex photoeliminations. United States. doi:10.2172/1313940.
Sharp, Paul. Fri . "Late transition metal m-or chemistry and D6 metal complex photoeliminations". United States. doi:10.2172/1313940. https://www.osti.gov/servlets/purl/1313940.
@article{osti_1313940,
title = {Late transition metal m-or chemistry and D6 metal complex photoeliminations},
author = {Sharp, Paul},
abstractNote = {With the goal of understanding and controlling photoreductive elimination reactions from d6 transition metal complexes as part of a solar energy storage cycle we have investigated the photochemistry of Pt(IV) bromo, chloro, hydroxo, and hydroperoxo complexes. Photoreductive elimination reactions occur for all of these complexes and appear to involve initial Pt-Br, Pt-Cl, or Pt-O bond fission. In the case of Pt-OH bond fission, the subsequent chemistry can be controlled through hydrogen bonding to the hydroxo group.},
doi = {10.2172/1313940},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Jul 31 00:00:00 EDT 2015},
month = {Fri Jul 31 00:00:00 EDT 2015}
}

Technical Report:

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  • The synthesis and reactions of late-transition-metal oxo and imido complexes was explored. The deprotonation of platinum(II) hydroxo complexes yielded new oxo complexes. Attempted deprotonation of Cp*Rh(III) hydroxo complexes did not give oxo complexes but complex mixtures probably resulting from reduction of the Rh(III) center. The reaction of Na/Hg with (Cp*RhCl{sub 2}){sub 2} gave the very reactive Rh(II) dimer, (Cp*RhCl){sub 2}. Rhodium(I) imido complexes with the bis(dimethylphosphino)methane ligand were prepared and found to be similar to the previously prepared bis(diphenylphosphino)methane complexes. Attempts to prepare bis(diphenylphosphino)methylamine, bis(diphenylphosphino)phenylamine, PMe{sub e} and NO{sup +} analogues were not successful. Attempts to prepare Cp*Rh(III) imido complexesmore » resulted in amido complexes and reduction. Rhodium (III) tris(3.5-dimethylpyrazoyl)borate analogues are reduction resistant but have not yet yielded imido complexes. The first imido complexes of Au were prepared by treating a Au oxo complex with amines or isocyanates. Dimeric Cp*Rh dioxygen and nitrosobenzene complexes were prepared by insertion into the Rh-Rh bond of (Cp*RhCl){sub 2}. The dioxygen complex activates a C-H bond of the Cp* ligand on treatment with PMe{sub 3}. Imido and oxo complexes nitrene and oxygen atom transfer product in reactions with CO. A novel electrophilic ring addition was observed with sterically protected aryl imido complexes. 15 refs.« less
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