Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

Benedict M Gardner; Gabor Balazs; Manfred Scheer; Ashley J Wooles; Floariana Tuna; Eric J L Mcinnes; Jonathan McMaster; William Lewis; Alexander J Blake; Stephen T Liddle

doi:10.1002/anie.201508600

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

Benedict M Gardner, Gabor Balazs, Manfred Scheer, Ashley J Wooles, Floariana Tuna, Eric J L Mcinnes, Jonathan McMaster, William Lewis, Alexander J Blake, Stephen T Liddle

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Abstract

he HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri 3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π∗-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form

Original language	English
Pages (from-to)	15250-15254
Number of pages	4
Journal	Angewandte Chemie (International Edition)
Volume	54
DOIs	https://doi.org/10.1002/anie.201508600
Publication status	Published - 28 Oct 2015

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@article{72b4a131c08240daa4d12ad67c1f455e,

title = "Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex",

abstract = "he HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri 3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π∗-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form",

author = "Gardner, {Benedict M} and Gabor Balazs and Manfred Scheer and Wooles, {Ashley J} and Floariana Tuna and Mcinnes, {Eric J L} and Jonathan McMaster and William Lewis and Blake, {Alexander J} and Liddle, {Stephen T}",

year = "2015",

month = oct,

day = "28",

doi = "10.1002/anie.201508600",

language = "English",

volume = "54",

pages = "15250--15254",

journal = "Angewandte Chemie (International Edition)",

issn = "1433-7851",

publisher = "John Wiley & Sons Ltd",

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TY - JOUR

T1 - Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

AU - Gardner, Benedict M

AU - Balazs, Gabor

AU - Scheer, Manfred

AU - Wooles, Ashley J

AU - Tuna, Floariana

AU - Mcinnes, Eric J L

AU - McMaster, Jonathan

AU - Lewis, William

AU - Blake, Alexander J

AU - Liddle, Stephen T

PY - 2015/10/28

Y1 - 2015/10/28

N2 - he HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri 3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π∗-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form

AB - he HAsAsH molecule has hitherto only been proposed tentatively as a short-lived species generated in electrochemical or microwave-plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(TrenTIPS)}2(μ-η2:η2-As2H2)] (3, TrenTIPS=N(CH2CH2NSiPri 3)3; Pri=CH(CH3)2). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back-bonding-type interactions from uranium to the HAsAsH π∗-orbital. This experimentally confirms the theoretically predicted excellent π-acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane-1,2-diide form

U2 - 10.1002/anie.201508600

DO - 10.1002/anie.201508600

M3 - Article

SN - 1433-7851

VL - 54

SP - 15250

EP - 15254

JO - Angewandte Chemie (International Edition)

JF - Angewandte Chemie (International Edition)

ER -

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

Abstract

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CCDC 1419459: Experimental Crystal Structure Determination

CCDC 1403870: Experimental Crystal Structure Determination

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Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

Abstract

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Datasets

CCDC 1419459: Experimental Crystal Structure Determination

CCDC 1403870: Experimental Crystal Structure Determination

Cite this