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The Nature of Bond Orbitals in Quadricovalent Complexes of Transition Elements

Kuhn, Hans (1948) The Nature of Bond Orbitals in Quadricovalent Complexes of Transition Elements. Journal of Chemical Physics, 16 (7). pp. 727-733. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20140805-135026748

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Abstract

In quadricovalent complexes of transition elements (Ni^(II), Pd^(II), Pt^(II), Au^(III), Ag^(II), Cu^(II)) the central atom uses four s or d orbitals of its outer shell for unshared electron pairs and two s or d and two p orbitals for bond formation. The problem here is to find the strongest possible four hybrid bond orbitals obtained by combining the two s—d and the two p orbitals available for bond formation. The strongest bond orbitals thus obtained are directed from the middle towards the four corners of a square, as it is expected from experimental evidence; they are composed of 4/9 s, 14/9 d, and two p orbitals, the strength being 2.943. These strongest possible orbitals are presumably used in complex of Ni^(II), Pt^(II), Au^(III), and Cu^(II), but probably not in complexes of Pd^(II) and Ag^(II); in the latter two cases there must be assumed square bond orbitals of composition s^nd^(2−n)p^2 with n somewhere between 1 and 4/9, i.e., orbitals of character between that of the strongest square bond orbitals of composition s^(4/9)d^(14/9)p^2 mentioned above and that of sdp^2 square orbitals discovered by Pauling.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1746980DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/16/7/10.1063/1.1746980PublisherArticle
Additional Information:© 1948 American Institute of Physics. Received 7 April 1948. The author is grateful to Professor Linus Pauling for many helpful suggestions and discussions and for the kind hospitality that he extended him during his stay in Pasadena. He also wishes to thank Dr. David P. Shoemaker for help in the preparation of the manuscript and to express his gratitude to the Swiss Foundation "Stiftung für Stipemdien auf dem Gebiete der Chemie" for fellowship.
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Stiftung für Stipemdien auf dem Gebiete der ChemieUNSPECIFIED
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Gates and Crellin Laboratories1187
Issue or Number:7
Record Number:CaltechAUTHORS:20140805-135026748
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140805-135026748
Official Citation:The Nature of Bond Orbitals in Quadricovalent Complexes of Transition Elements Kuhn, Hans, The Journal of Chemical Physics, 16, 727-733 (1948), DOI:http://dx.doi.org/10.1063/1.1746980
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:48000
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:05 Aug 2014 22:30
Last Modified:03 Oct 2019 06:59

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