On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3

Somia E. Bajwa; Thomas E. Storr; Lauren E. Hatcher; Thomas J. Williams; Christoph G. Baumann; Adrian C. Whitwood; David R. Allan; Simon J. Teat; Paul R. Raithby; Ian J. S. Fairlamb

doi:10.1039/c2sc01050j

On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3

Somia E. Bajwa, Thomas E. Storr, Lauren E. Hatcher, Thomas J. Williams, Christoph G. Baumann, Adrian C. Whitwood, David R. Allan, Simon J. Teat, Paul R. Raithby, Ian J. S. Fairlamb

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

Abstract

Pd-3(OAc)(5)NO2, an impurity in "Pd(OAc)(2)" {formally Pd-3(OAc)(6)}, emerges as a serious issue in the synthesis of pure Pd-II complexes derived from Pd(OAc)(2), for example in our C-H activation precatalyst, Pd(OAc)(2)(pip)(2) (pip piperidine). A previous proposal that nitrite anion can be formed by oxidation of CH3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO2)(C boolean AND N) L (C boolean AND N = papaverine; L = CH3CN or DMSO) can be explained by Pd-3(OAc)(5)NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(eta(1)-ONO)(C boolean AND N)PPh3 has been observed.

Original language	English
Pages (from-to)	1656-1661
Number of pages	6
Journal	Chemical Science
Volume	3
Issue number	5
DOIs	https://doi.org/10.1039/c2sc01050j
Publication status	Published - May 2012

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10.1039/c2sc01050j

http://pubs.rsc.org/en/Content/ArticleLanding/2012/SC/c2sc01050j

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Bajwa, S. E., Storr, T. E., Hatcher, L. E., Williams, T. J., Baumann, C. G., Whitwood, A. C., Allan, D. R., Teat, S. J., Raithby, P. R., & Fairlamb, I. J. S. (2012). On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3. Chemical Science, 3(5), 1656-1661. https://doi.org/10.1039/c2sc01050j

@article{d8ed62690aa24259a1d52e60e23c90e2,

title = "On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3",

abstract = "Pd-3(OAc)(5)NO2, an impurity in {"}Pd(OAc)(2){"} {formally Pd-3(OAc)(6)}, emerges as a serious issue in the synthesis of pure Pd-II complexes derived from Pd(OAc)(2), for example in our C-H activation precatalyst, Pd(OAc)(2)(pip)(2) (pip piperidine). A previous proposal that nitrite anion can be formed by oxidation of CH3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO2)(C boolean AND N) L (C boolean AND N = papaverine; L = CH3CN or DMSO) can be explained by Pd-3(OAc)(5)NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(eta(1)-ONO)(C boolean AND N)PPh3 has been observed.",

author = "Bajwa, {Somia E.} and Storr, {Thomas E.} and Hatcher, {Lauren E.} and Williams, {Thomas J.} and Baumann, {Christoph G.} and Whitwood, {Adrian C.} and Allan, {David R.} and Teat, {Simon J.} and Raithby, {Paul R.} and Fairlamb, {Ian J. S.}",

year = "2012",

month = may,

doi = "10.1039/c2sc01050j",

language = "English",

volume = "3",

pages = "1656--1661",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "The Royal Society of Chemistry",

number = "5",

}

Bajwa, SE, Storr, TE, Hatcher, LE, Williams, TJ, Baumann, CG, Whitwood, AC, Allan, DR, Teat, SJ, Raithby, PR & Fairlamb, IJS 2012, 'On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3', Chemical Science, vol. 3, no. 5, pp. 1656-1661. https://doi.org/10.1039/c2sc01050j

On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3. / Bajwa, Somia E.; Storr, Thomas E.; Hatcher, Lauren E. et al.
In: Chemical Science, Vol. 3, No. 5, 05.2012, p. 1656-1661.

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

TY - JOUR

T1 - On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2)

T2 - photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3

AU - Bajwa, Somia E.

AU - Storr, Thomas E.

AU - Hatcher, Lauren E.

AU - Williams, Thomas J.

AU - Baumann, Christoph G.

AU - Whitwood, Adrian C.

AU - Allan, David R.

AU - Teat, Simon J.

AU - Raithby, Paul R.

AU - Fairlamb, Ian J. S.

PY - 2012/5

Y1 - 2012/5

N2 - Pd-3(OAc)(5)NO2, an impurity in "Pd(OAc)(2)" {formally Pd-3(OAc)(6)}, emerges as a serious issue in the synthesis of pure Pd-II complexes derived from Pd(OAc)(2), for example in our C-H activation precatalyst, Pd(OAc)(2)(pip)(2) (pip piperidine). A previous proposal that nitrite anion can be formed by oxidation of CH3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO2)(C boolean AND N) L (C boolean AND N = papaverine; L = CH3CN or DMSO) can be explained by Pd-3(OAc)(5)NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(eta(1)-ONO)(C boolean AND N)PPh3 has been observed.

AB - Pd-3(OAc)(5)NO2, an impurity in "Pd(OAc)(2)" {formally Pd-3(OAc)(6)}, emerges as a serious issue in the synthesis of pure Pd-II complexes derived from Pd(OAc)(2), for example in our C-H activation precatalyst, Pd(OAc)(2)(pip)(2) (pip piperidine). A previous proposal that nitrite anion can be formed by oxidation of CH3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO2)(C boolean AND N) L (C boolean AND N = papaverine; L = CH3CN or DMSO) can be explained by Pd-3(OAc)(5)NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(eta(1)-ONO)(C boolean AND N)PPh3 has been observed.

UR - http://www.scopus.com/inward/record.url?scp=84859336806&partnerID=8YFLogxK

U2 - 10.1039/c2sc01050j

DO - 10.1039/c2sc01050j

M3 - Article

SN - 2041-6520

VL - 3

SP - 1656

EP - 1661

JO - Chemical Science

JF - Chemical Science

IS - 5

ER -

On the appearance of nitrite anion in [PdX(OAc)L-2] and [Pd(X)(C boolean AND N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(eta(1)-ONO)(C boolean AND N)PPh3

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