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Relationship of cis-diammineplatinum α-pyridone blue to other platinum blues. An x-ray photoelectron study

Barton, J. K. and Best, S. A. and Lippard, S. J. and Walton, R. A. (1978) Relationship of cis-diammineplatinum α-pyridone blue to other platinum blues. An x-ray photoelectron study. Journal of the American Chemical Society, 100 (12). pp. 3785-3788. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170707-180501544

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Abstract

The x-ray photoelectron spectrum (XPS) of crystalline cis-diammineplatinum a-pyridone blue, [Pt_2(NH_3)_4(C_5H_4ON)_2]_2(NO_3)_5, has been investigated and the Pt 4f binding energies of this complex found to be similar to those exhibited by Pt(II) complexes such as cis-(H_3N)_2PtCl_2. This result is in accord with the previous assignment of a formal platinum oxidation state of 2.25 in the blue a-pyridone complex. The widths of the Pt 4f peaks (fwhm ~ 1.3) indicate that the binding energies associated with the two geometrically different types of Pt environments in the α-pyridone oligomer are very similar, the implication being that within the Pt4 unit there must be a considerable delocalization of charge. A comparison of the XPS data for the α-pyridone blue with that found for the platinum uracil and acetamide blues shows that these species have similar electronic structures, there being no evidence that they are pure derivatives of Pt(IV). The XPS of some samples of the acetamide blue ("Platinblau") show the presence of small amounts of higher oxidation state contaminants, consistent with the difficulty in preparing this species in a reproducibly pure form. The Pt(III) dimer K_2Pt_2(SO_4)_4·3H_2O possesses Pt 4f binding energies which are much closer to those of coordination complexes of Pt(IV) than Pt(II).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00480a022DOIArticle
http://pubs.acs.org/doi/pdf/10.1021/ja00480a022PublisherArticle
ORCID:
AuthorORCID
Barton, J. K.0000-0001-9883-1600
Additional Information:© 1978 American Chemical Society. Received November 14, 1977 This work was supported by research grants from the National Science Foundation (Grant CHE74-12788A02 to R.A.W.) and the National Cancer Institute, DHEW (Grant CA-15826 to S.J.L.). J.K.B. is the recipient of a National Science Foundation Predoctoral Fellowship. A generous loan of K_2PtC_(14) from Engelhard Industries is gratefully acknowledged.
Funders:
Funding AgencyGrant Number
NSFCHE74-12788A02
NIHCA-15826
Engelhard IndustriesUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20170707-180501544
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170707-180501544
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78876
Collection:CaltechAUTHORS
Deposited By: Donna Wrublewski
Deposited On:10 Jul 2017 17:00
Last Modified:03 Oct 2019 18:13

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