@article {2124,
	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},
	journal = {Inorganic Chemistry},
	volume = {44},
	number = {7},
	year = {2005},
	note = {Times Cited: 7Bennett, MA Bhargava, SK Boas, JF Boere, RT Bond, AM Edwards, AJ Guo, SX Hammerl, A Pilbrow, JR Priver, SH Schwerdtfeger, P},
	month = {Apr},
	pages = {2472-2482},
	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(+).},
	isbn = {0020-1669},
	url = {<Go to ISI>://WOS:000228054200046},
	author = {Bennett, M. A. and Bhargava, S. K. and Boas, J. F. and Boer{\'e}, R. T. and Bond, A. M. and Edwards, A. J. and Guo, S. X. and Hammerl, A. and Pilbrow, J. R. and Priver, S. H. and Schwerdtfeger, P.}
}
