Computational insight into the reductive oligomerisation of CO at uranium(III) mixed-sandwich complexes

David McKay; Alistair S. P. Frey; Jennifer C. Green; F. Geoffrey N. Cloke; Laurent Maron

doi:10.1039/c2cc30864a

Computational insight into the reductive oligomerisation of CO at uranium(III) mixed-sandwich complexes

David McKay, Alistair S. P. Frey, Jennifer C. Green, F. Geoffrey N. Cloke, Laurent Maron^*

^*Corresponding author for this work

School of Chemistry

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

Abstract

Calculations reveal a multistep pathway towards formation of linear [U](2)-(mu-eta(1):eta(1)-C2O2); [U] = U(eta-C8H6{SiH3-1,4}(2))(eta-Cp). However formation of deltate-bridged [U](2)-(mu-eta(1):eta(2)-C3O3) requires an alternative mechanism, involving a side-on [U](2)-(mu-eta(2):eta(2)-CO) complex and whereby the bridging units of [U](2)-(mu-eta(2):eta(2)-CnOn) intermediates (n = 1, 2) react directly with free CO.

Original language	English
Pages (from-to)	4118-4120
Number of pages	3
Journal	Chemical Communications
Volume	48
Issue number	34
DOIs	https://doi.org/10.1039/c2cc30864a
Publication status	Published - 2012

Keywords

CARBON-MONOXIDE
DINITROGEN
HYDROGENATION
1,2-ADDITION
REACTIVITY
ACTIVATION
MECHANISM
BINDING
N-2

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title = "Computational insight into the reductive oligomerisation of CO at uranium(III) mixed-sandwich complexes",

abstract = "Calculations reveal a multistep pathway towards formation of linear [U](2)-(mu-eta(1):eta(1)-C2O2); [U] = U(eta-C8H6{SiH3-1,4}(2))(eta-Cp). However formation of deltate-bridged [U](2)-(mu-eta(1):eta(2)-C3O3) requires an alternative mechanism, involving a side-on [U](2)-(mu-eta(2):eta(2)-CO) complex and whereby the bridging units of [U](2)-(mu-eta(2):eta(2)-CnOn) intermediates (n = 1, 2) react directly with free CO.",

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author = "David McKay and Frey, {Alistair S. P.} and Green, {Jennifer C.} and Cloke, {F. Geoffrey N.} and Laurent Maron",

year = "2012",

doi = "10.1039/c2cc30864a",

language = "English",

volume = "48",

pages = "4118--4120",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

number = "34",

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TY - JOUR

T1 - Computational insight into the reductive oligomerisation of CO at uranium(III) mixed-sandwich complexes

AU - McKay, David

AU - Frey, Alistair S. P.

AU - Green, Jennifer C.

AU - Cloke, F. Geoffrey N.

AU - Maron, Laurent

PY - 2012

Y1 - 2012

N2 - Calculations reveal a multistep pathway towards formation of linear [U](2)-(mu-eta(1):eta(1)-C2O2); [U] = U(eta-C8H6{SiH3-1,4}(2))(eta-Cp). However formation of deltate-bridged [U](2)-(mu-eta(1):eta(2)-C3O3) requires an alternative mechanism, involving a side-on [U](2)-(mu-eta(2):eta(2)-CO) complex and whereby the bridging units of [U](2)-(mu-eta(2):eta(2)-CnOn) intermediates (n = 1, 2) react directly with free CO.

AB - Calculations reveal a multistep pathway towards formation of linear [U](2)-(mu-eta(1):eta(1)-C2O2); [U] = U(eta-C8H6{SiH3-1,4}(2))(eta-Cp). However formation of deltate-bridged [U](2)-(mu-eta(1):eta(2)-C3O3) requires an alternative mechanism, involving a side-on [U](2)-(mu-eta(2):eta(2)-CO) complex and whereby the bridging units of [U](2)-(mu-eta(2):eta(2)-CnOn) intermediates (n = 1, 2) react directly with free CO.

KW - CARBON-MONOXIDE

KW - DINITROGEN

KW - HYDROGENATION

KW - 1,2-ADDITION

KW - REACTIVITY

KW - ACTIVATION

KW - MECHANISM

KW - BINDING

KW - N-2

U2 - 10.1039/c2cc30864a

DO - 10.1039/c2cc30864a

M3 - Article

SN - 1359-7345

VL - 48

SP - 4118

EP - 4120

JO - Chemical Communications

JF - Chemical Communications

IS - 34

ER -

Computational insight into the reductive oligomerisation of CO at uranium(III) mixed-sandwich complexes

Abstract

Keywords

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