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Title: Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

Abstract

In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)V≡N(X)] formulation [nacnac = (Ar)NC(Me)CHC(Me)(Ar) -, Ar = 2,6-(CHMe 2) 2C 6H 3); X– = OAr (1) and N(4-Me-C 6H 4) 2 (Ntolyl 2) (2)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H 2SiPh 2, readily converts the nitride ligand in 1 into a primary silyl–amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)V{N(H)SiHPh 2}(OAr)] (3). Likewise, addition of the B–H bond in pinacolborane to the nitride moiety in 2 results in formation of the boryl–amide complex [(nacnac)V{N(H)B(pinacol)}(Ntolyl 2)] (4). In addition to spectroscopic data, complexes 3 and 4 were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of 1 with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na] 2[(nacnac)V(N)(OAr)] 2 (5), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1353234
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 54; Journal Issue: 6
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Thompson, Rick, Tran, Ba L., Ghosh, Soumya, Chen, Chun-Hsing, Pink, Maren, Gao, Xinfeng, Carroll, Patrick J., Baik, Mu-Hyun, and Mindiola, Daniel J.. Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b00302.
Thompson, Rick, Tran, Ba L., Ghosh, Soumya, Chen, Chun-Hsing, Pink, Maren, Gao, Xinfeng, Carroll, Patrick J., Baik, Mu-Hyun, & Mindiola, Daniel J.. Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes. United States. doi:10.1021/acs.inorgchem.5b00302.
Thompson, Rick, Tran, Ba L., Ghosh, Soumya, Chen, Chun-Hsing, Pink, Maren, Gao, Xinfeng, Carroll, Patrick J., Baik, Mu-Hyun, and Mindiola, Daniel J.. Mon . "Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes". United States. doi:10.1021/acs.inorgchem.5b00302.
@article{osti_1353234,
title = {Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes},
author = {Thompson, Rick and Tran, Ba L. and Ghosh, Soumya and Chen, Chun-Hsing and Pink, Maren and Gao, Xinfeng and Carroll, Patrick J. and Baik, Mu-Hyun and Mindiola, Daniel J.},
abstractNote = {In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)V≡N(X)] formulation [nacnac = (Ar)NC(Me)CHC(Me)(Ar)-, Ar = 2,6-(CHMe2)2C6H3); X– = OAr (1) and N(4-Me-C6H4)2 (Ntolyl2) (2)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H2SiPh2, readily converts the nitride ligand in 1 into a primary silyl–amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)V{N(H)SiHPh2}(OAr)] (3). Likewise, addition of the B–H bond in pinacolborane to the nitride moiety in 2 results in formation of the boryl–amide complex [(nacnac)V{N(H)B(pinacol)}(Ntolyl2)] (4). In addition to spectroscopic data, complexes 3 and 4 were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of 1 with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na]2[(nacnac)V(N)(OAr)]2 (5), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies.},
doi = {10.1021/acs.inorgchem.5b00302},
journal = {Inorganic Chemistry},
number = 6,
volume = 54,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2015},
month = {Mon Mar 02 00:00:00 EST 2015}
}