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

S E Bajwa; T E Storr; Lauren E Hatcher; T J Williams; C G Baumann; A C Whitwood; D R Allan; S J Teat; Paul R Raithby; I 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

S E Bajwa, T E Storr, Lauren E Hatcher, T J Williams, C G Baumann, A C Whitwood, D R Allan, S J Teat, Paul R Raithby, I J S Fairlamb

Department of Chemistry

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

33 Citations (Scopus)

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Abstract

Pd 3(OAc) 5NO 2, 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 CH 3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO 2)(C∧N)L (C∧N = papaverine; L = CH 3CN or DMSO) can be explained by Pd 3(OAc) 5NO 2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η 1-ONO)(C∧N)PPh 3 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 - May 2012

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Senior Fellowship - TIME RESOLVED CRYSTALLOGRAPHY
Raithby, P.
Engineering and Physical Sciences Research Council
1/12/06 → 30/11/11
Project: Research council

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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)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

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. / Bajwa, S E; Storr, T E; Hatcher, Lauren E; Williams, T J; Baumann, C G; Whitwood, A C; Allan, D R; Teat, S J; Raithby, Paul R; Fairlamb, I J S.

In: Chemical Science, Vol. 3, No. 5, 05.2012, p. 1656-1661.

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

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

Bajwa, S E ; Storr, T E ; Hatcher, Lauren E ; Williams, T J ; Baumann, C G ; Whitwood, A C ; Allan, D R ; Teat, S J ; Raithby, Paul R ; Fairlamb, I J S. / 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. In: Chemical Science. 2012 ; Vol. 3, No. 5. pp. 1656-1661.

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abstract = "Pd 3(OAc) 5NO 2, 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 CH 3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO 2)(C∧N)L (C∧N = papaverine; L = CH 3CN or DMSO) can be explained by Pd 3(OAc) 5NO 2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η 1-ONO)(C∧N)PPh 3 has been observed.",

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AU - Hatcher, Lauren E

AU - Williams, T J

AU - Baumann, C G

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AU - Allan, D R

AU - Teat, S J

AU - Raithby, Paul R

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AB - Pd 3(OAc) 5NO 2, 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 CH 3CN by metallic Pd and air, leading to cyclo(ortho)palladated complexes containing nitrite anion, e.g. Pd(NO 2)(C∧N)L (C∧N = papaverine; L = CH 3CN or DMSO) can be explained by Pd 3(OAc) 5NO 2 acting as the nitrite source. Finally, photocrystallographic metastable linkage isomerisation and complete conversion to an oxygen-bound nitrito complex Pd(η 1-ONO)(C∧N)PPh 3 has been observed.

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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

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Senior Fellowship - TIME RESOLVED CRYSTALLOGRAPHY

Cite this

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