On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^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)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^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

Chemistry of Materials and Catalysis

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

46 Citations (Scopus)

Abstract

Pd3(OAc)5NO2, an impurity in “Pd(OAc)2” {formally Pd3(OAc)6}, emerges as a serious issue in the synthesis of pure PdII 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^N)L (C^N = papaverine; L = CH3CN or DMSO) can be explained by Pd3(OAc)5NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η1-ONO)(C^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
Early online date	23 Feb 2012
DOIs	https://doi.org/10.1039/c2sc01050j
Publication status	Published - 2012

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10.1039/c2sc01050j

Cite this

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)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^N)PPh3. Chemical Science, 3(5), 1656-1661. https://doi.org/10.1039/c2sc01050j

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title = "On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^N)PPh3",

abstract = "Pd3(OAc)5NO2, an impurity in “Pd(OAc)2” {formally Pd3(OAc)6}, emerges as a serious issue in the synthesis of pure PdII 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^N)L (C^N = papaverine; L = CH3CN or DMSO) can be explained by Pd3(OAc)5NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η1-ONO)(C^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",

doi = "10.1039/c2sc01050j",

language = "English",

volume = "3",

pages = "1656--1661",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "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)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^N)PPh3', Chemical Science, vol. 3, no. 5, pp. 1656-1661. https://doi.org/10.1039/c2sc01050j

TY - JOUR

T1 - On the appearance of nitrite anion in [PdX(OAc)L2] and [Pd(X)(C^N)L] syntheses (X = OAc or NO2): photocrystallographic identification of metastable Pd(η1-ONO)(C^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

Y1 - 2012

N2 - Pd3(OAc)5NO2, an impurity in “Pd(OAc)2” {formally Pd3(OAc)6}, emerges as a serious issue in the synthesis of pure PdII 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^N)L (C^N = papaverine; L = CH3CN or DMSO) can be explained by Pd3(OAc)5NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η1-ONO)(C^N)PPh3 has been observed.

AB - Pd3(OAc)5NO2, an impurity in “Pd(OAc)2” {formally Pd3(OAc)6}, emerges as a serious issue in the synthesis of pure PdII 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^N)L (C^N = papaverine; L = CH3CN or DMSO) can be explained by Pd3(OAc)5NO2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η1-ONO)(C^N)PPh3 has been observed.

U2 - 10.1039/c2sc01050j

DO - 10.1039/c2sc01050j

M3 - Article

VL - 3

SP - 1656

EP - 1661

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 5

ER -