skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Transition metal mediated transformations of small molecules

Abstract

Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.

Authors:
 [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1346019
Report Number(s):
DOE-PSU-13295-2
DOE Contract Number:
FG02-84ER13295
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; Catalysis; Transition metals; Polymerization; Biomass; Green chemistry; Carbon dioxide

Citation Formats

Sen, Ayusman. Transition metal mediated transformations of small molecules. United States: N. p., 2017. Web. doi:10.2172/1346019.
Sen, Ayusman. Transition metal mediated transformations of small molecules. United States. doi:10.2172/1346019.
Sen, Ayusman. Wed . "Transition metal mediated transformations of small molecules". United States. doi:10.2172/1346019. https://www.osti.gov/servlets/purl/1346019.
@article{osti_1346019,
title = {Transition metal mediated transformations of small molecules},
author = {Sen, Ayusman},
abstractNote = {Catalysis at metal centers is of great scientific, as well as practical, importance because of the high efficiency, high specificity, and low energy demands often associated with such systems. The two major themes of our research are (a) the design of metal-based systems for the synthesis of novel classes of polymers and (b) the identification of new metal-catalyzed systems for the conversion of biomass to fuels and chemicals, and related “green” chemical processes.},
doi = {10.2172/1346019},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Mar 08 00:00:00 EST 2017},
month = {Wed Mar 08 00:00:00 EST 2017}
}

Technical Report:

Save / Share:
  • Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of [alpha]-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors whenmore » doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.« less
  • We have succeeded in extending the palladium(2) catalyzed alternating copolyermization of carbon monoxide with olefins to include {alpha}-olefins. The second aspect of the use of carbon monoxide as a reactive monomer that we have studied is the catalytic synthesis of polyoxamide and polyurea from {alpha},{omega}-diamines and carbon monoxide. An important application of the new catalysts was in the linear step-growth polymerization of p-divinylbenzene. In order to arrive at an understanding of the elementary steps are involved in the Mo(6) oxide catalyzed oxidation of alkanes and olefins, we have examined the anaerobic and aerobic decomposition routes for Mo(6)-oxoalkyl complexes of themore » type, (Me{sub 2}-bipy){sub 2}Mo{O}{sub 2}(R){sub 2}. We have investigated the oxidation of ethers by the platinum(2) ion and by metallic platinum in aqueous medium. Finally, we have examined ways to synthesize metal oxide nanoclusters of well-defined sizes in polymeric matrices. 10 refs.« less
  • The progress report summarizes the work done in the first 6 months of the current period. During this time we have worked on three different facets of organotransition metal chemistry and homogeneous catalysis and our results to data are briefly summarized. In a series of experiments, we have observed and studied the insertion of a number of olefins into the Pd(II)-COR bonds of the cationic and neutral compounds, trans-Pd(PPh{sub 3}){sub 2}(MeCN)(COR){sup +}BF{sub 4}{sup {minus}} and trans-Pd(PPh{sub 3}){sub 2}(Cl)(COR), respectively.
  • Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of {alpha}-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors whenmore » doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.« less
  • The catalysis of organic transformations by soluble transition metal compounds has gained widespread attention because of the high efficiency, high specificity and low energy demands often associated with such systems. Research goals in this area are: (a) to achieve a fundamental mechanistic understanding of the important homogeneous catalytic systems and, (b) to use this knowledge to develop new and useful catalytic processes. We have focused on four broad areas of transition metal catalyzed/mediated transformations of organic molecules: (a) the selective functionalization of alkanes and arenas by electrophilic metal compounds, (b) the coupling of organic mono- and dihalides by low-valent, anionic,more » metal complexes, (c) transition metal mediated/catalyzed reactions of carbon monoxide, and (d) the oxidation chemistry of high-valent organometallic oxo complexes. Results are briefly summarized below.« less