DFT studies on reactions of CO2 with niobium and vanadium nitride complexes

Congjie Zhang; Meiyan Wang; Liqin Xue; Ting Fan; Zhenyang Lin

doi:10.1021/om2007584

DFT studies on reactions of CO₂ with niobium and vanadium nitride complexes

Congjie Zhang^*, Meiyan Wang, Liqin Xue, Ting Fan, Zhenyang Lin

^*Corresponding author for this work

Research output: Contribution to journal › Journal Article › peer-review

15 Citations (Scopus)

Abstract

We have investigated the reduction of CO₂ to CO mediated by the anionic niobium nitride complex [NNb(N^tBuMe)₃], a model complex of [NNb(N^tBuAr)₃], using density functional theory. We mainly calculated the energetics for the interesting reaction sequence, reported recently by Cummins and his co-workers, involving reactions of the anionic niobium nitride complex [NNb(N^tBuAr)₃] with CO₂ to first give a carbamate complex. The carbamate complex then reacts with MeC(O)Cl to give an isocyanateacetate, which can be reduced by SmI₂ to give the isocyanate complex (OCN)Nb(N^tBuAr) ₃. Further reduction of the isocyanate complex by Na/Hg extrudes CO and regenerates [NNb(N^tBuAr)₃]. In addition, we compare the reaction pathways for the reduction reaction of the isocyanate complexes (OCN)M(N^tBuMe)₃ (M = Nb, V), model complexes of (OCN)M(N^tBuAr)₃, with sodium and explain why these two reduction reactions give remarkably different products.

Original language	English
Pages (from-to)	5911-5918
Number of pages	8
Journal	Organometallics
Volume	30
Issue number	21
DOIs	https://doi.org/10.1021/om2007584
Publication status	Published - 14 Nov 2011
Externally published	Yes

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@article{58ce1ae8b5864c7587bb323ff9492ae8,

title = "DFT studies on reactions of CO2 with niobium and vanadium nitride complexes",

abstract = "We have investigated the reduction of CO2 to CO mediated by the anionic niobium nitride complex [NNb(NtBuMe)3], a model complex of [NNb(NtBuAr)3], using density functional theory. We mainly calculated the energetics for the interesting reaction sequence, reported recently by Cummins and his co-workers, involving reactions of the anionic niobium nitride complex [NNb(NtBuAr)3] with CO2 to first give a carbamate complex. The carbamate complex then reacts with MeC(O)Cl to give an isocyanateacetate, which can be reduced by SmI2 to give the isocyanate complex (OCN)Nb(NtBuAr) 3. Further reduction of the isocyanate complex by Na/Hg extrudes CO and regenerates [NNb(NtBuAr)3]. In addition, we compare the reaction pathways for the reduction reaction of the isocyanate complexes (OCN)M(NtBuMe)3 (M = Nb, V), model complexes of (OCN)M(NtBuAr)3, with sodium and explain why these two reduction reactions give remarkably different products.",

author = "Congjie Zhang and Meiyan Wang and Liqin Xue and Ting Fan and Zhenyang Lin",

year = "2011",

month = nov,

day = "14",

doi = "10.1021/om2007584",

language = "English",

volume = "30",

pages = "5911--5918",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - DFT studies on reactions of CO2 with niobium and vanadium nitride complexes

AU - Zhang, Congjie

AU - Wang, Meiyan

AU - Xue, Liqin

AU - Fan, Ting

AU - Lin, Zhenyang

PY - 2011/11/14

Y1 - 2011/11/14

N2 - We have investigated the reduction of CO2 to CO mediated by the anionic niobium nitride complex [NNb(NtBuMe)3], a model complex of [NNb(NtBuAr)3], using density functional theory. We mainly calculated the energetics for the interesting reaction sequence, reported recently by Cummins and his co-workers, involving reactions of the anionic niobium nitride complex [NNb(NtBuAr)3] with CO2 to first give a carbamate complex. The carbamate complex then reacts with MeC(O)Cl to give an isocyanateacetate, which can be reduced by SmI2 to give the isocyanate complex (OCN)Nb(NtBuAr) 3. Further reduction of the isocyanate complex by Na/Hg extrudes CO and regenerates [NNb(NtBuAr)3]. In addition, we compare the reaction pathways for the reduction reaction of the isocyanate complexes (OCN)M(NtBuMe)3 (M = Nb, V), model complexes of (OCN)M(NtBuAr)3, with sodium and explain why these two reduction reactions give remarkably different products.

AB - We have investigated the reduction of CO2 to CO mediated by the anionic niobium nitride complex [NNb(NtBuMe)3], a model complex of [NNb(NtBuAr)3], using density functional theory. We mainly calculated the energetics for the interesting reaction sequence, reported recently by Cummins and his co-workers, involving reactions of the anionic niobium nitride complex [NNb(NtBuAr)3] with CO2 to first give a carbamate complex. The carbamate complex then reacts with MeC(O)Cl to give an isocyanateacetate, which can be reduced by SmI2 to give the isocyanate complex (OCN)Nb(NtBuAr) 3. Further reduction of the isocyanate complex by Na/Hg extrudes CO and regenerates [NNb(NtBuAr)3]. In addition, we compare the reaction pathways for the reduction reaction of the isocyanate complexes (OCN)M(NtBuMe)3 (M = Nb, V), model complexes of (OCN)M(NtBuAr)3, with sodium and explain why these two reduction reactions give remarkably different products.

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:000296487100045

UR - https://openalex.org/W2327779520

UR - https://www.scopus.com/pages/publications/80755130094

U2 - 10.1021/om2007584

DO - 10.1021/om2007584

M3 - Journal Article

SN - 0276-7333

VL - 30

SP - 5911

EP - 5918

JO - Organometallics

JF - Organometallics

IS - 21

ER -

DFT studies on reactions of CO₂ with niobium and vanadium nitride complexes

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