Electrochemically informed synthesis and characterization of salts of the [Pt-2(mu-kAs,kC-C6H3-5-Me-2-AsPh2)(4)](+) lantern complex containing a pt-pt bond of order 1/2

Bennett, M, Bhargava, S, Boas, J, Boere, R, Bond, A, Edwards, A, Guo, S, Hammerl, A, Pilbrow, J, Priver, S and Schwerdtfeger, P 2005, 'Electrochemically informed synthesis and characterization of salts of the [Pt-2(mu-kAs,kC-C6H3-5-Me-2-AsPh2)(4)](+) lantern complex containing a pt-pt bond of order 1/2', Inorganic Chemistry, vol. 44, no. 7, pp. 2472-2482.


Document type: Journal Article
Collection: Journal Articles

Title Electrochemically informed synthesis and characterization of salts of the [Pt-2(mu-kAs,kC-C6H3-5-Me-2-AsPh2)(4)](+) lantern complex containing a pt-pt bond of order 1/2
Author(s) Bennett, M
Bhargava, S
Boas, J
Boere, R
Bond, A
Edwards, A
Guo, S
Hammerl, A
Pilbrow, J
Priver, S
Schwerdtfeger, P
Year 2005
Journal name Inorganic Chemistry
Volume number 44
Issue number 7
Start page 2472
End page 2482
Total pages 11
Publisher American Chemical Society
Abstract Detailed electrochemical studies in dichloromethane (0.1 M BU4NPF6) on the oxidation of the half-lantern [Pt-2-((KAs)-As-2,C -C6H3-5-Me-2-AsPh2)(2)(mu-KAS,KC-C6H3-5-Me-2-AsPh2)(2)] (1) and full-lantern [Pt-2(mu-KAS,KC-C6H3-5-Me-2-AsPh2)(4)] (2) complexes reveal the presence of an exceptionally stable dinuclear Pt cation 2(+). Thus, oxidation of 1 occurs on the voltammetric time scale via a ladder-square scheme to give 2(+), whereas 2 is directly converted to 2(+). Electrochemically informed chemical synthesis enabled the isolation of solid [2(+)][BF4-] to be achieved. Single-crystal X-ray structural analysis showed that 2(+) also has a lantern structure but with a shorter separation between the Pt centers [2.7069(3) angstrom (2(+)), 2.8955(4) angstrom (2)]. EPR spectra of 2(+) provide unequivocal evidence for axial symmetry of the complex and are noteworthy because of an exceptionally large, nearly isotropic hyperfine coupling constant of about 0.1 cm(-1). Spectroscopic data support the conclusion that the unpaired electron in the 2(+) cation is distributed equally between the two Pt nuclei and imply that oxidation of 2 to 2(+) leads to the establishment of the metal-tometal hemibond. Results of extended Huckel molecular orbital and density functional calculations on 2 and 2(+) lead to the conclusions that s, p, d2/z mixing of orbitals contributes to the large EPR Pt hyperfine coupling and also that the structural adjustments that occur upon removal of an electron from 2 are driven by the metal-metal bonding character present in 2(+).
Subject Chemical Engineering not elsewhere classified
Keyword(s) Chemistry
Inorganic
Nuclear
DOI - identifier 10.1021/ic048660i
Copyright notice Copyright © 2005 American Chemical Society
ISSN 0020-1669
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