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Title: Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation

Abstract

The encumbered tetraisocyanide dianion Na2[Fe-(CNArMes2)4] reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2–). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono-CO2 adduct. This results in the formation of four-coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment of an C(O)OSiR3 group to an isocyanide nitrogen atom. In this work, crystallographic, spectroscopic, and computational analyses of these iron–carbon multiply bonded species reveal electronic structure properties indicative of a conformationally locked iron carbyne unit.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
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  1. Univ. of California, San Diego, La Jolla, CA (United States)
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); W. M. Keck Foundation
OSTI Identifier:
1533117
Alternate Identifier(s):
OSTI ID: 1376752
Grant/Contract Number:  
SC0008058
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 36; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; carbon dioxide; carbynes; iron; isocyanides; multiple bonds

Citation Formats

Mokhtarzadeh, Charles C., Moore, Curtis E., Rheingold, Arnold L., and Figueroa, Joshua S. Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation. United States: N. p., 2017. Web. doi:10.1002/anie.201705877.
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Mokhtarzadeh, Charles C., Moore, Curtis E., Rheingold, Arnold L., & Figueroa, Joshua S. Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation. United States. https://doi.org/10.1002/anie.201705877
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Mokhtarzadeh, Charles C., Moore, Curtis E., Rheingold, Arnold L., and Figueroa, Joshua S. Mon . "Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation". United States. https://doi.org/10.1002/anie.201705877. https://www.osti.gov/servlets/purl/1533117.
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@article{osti_1533117,
title = {Terminal Iron Carbyne Complexes Derived from Arrested CO2 Reductive Disproportionation},
author = {Mokhtarzadeh, Charles C. and Moore, Curtis E. and Rheingold, Arnold L. and Figueroa, Joshua S.},
abstractNote = {The encumbered tetraisocyanide dianion Na2[Fe-(CNArMes2)4] reacts with two molecules of CO2 to effect reductive disproportionation to CO and carbonate ([CO3]2–). When the reaction is performed in the presence of silyl triflates, reductive disproportionation is arrested by silylative esterification of a mono-CO2 adduct. This results in the formation of four-coordinate terminal iron carbynes possessing an aryl carbamate substituent owing to the direct attachment of an C(O)OSiR3 group to an isocyanide nitrogen atom. In this work, crystallographic, spectroscopic, and computational analyses of these iron–carbon multiply bonded species reveal electronic structure properties indicative of a conformationally locked iron carbyne unit.},
doi = {10.1002/anie.201705877},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 56,
place = {United States},
year = {Mon Jul 03 00:00:00 EDT 2017},
month = {Mon Jul 03 00:00:00 EDT 2017}
}
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https://doi.org/10.1002/anie.201705877
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