DC Field | Value | Language |
---|---|---|
dc.contributor.author | Hossain, Ferdaus | ko |
dc.contributor.author | Rigsby, Matthew A. | ko |
dc.contributor.author | Duncan, Cole T. | ko |
dc.contributor.author | Milligan, Paul L., Jr. | ko |
dc.contributor.author | Lord, Richard L. | ko |
dc.contributor.author | Baik, Mu-Hyun | ko |
dc.contributor.author | Schultz, Franklin A. | ko |
dc.date.accessioned | 2016-04-12T07:40:37Z | - |
dc.date.available | 2016-04-12T07:40:37Z | - |
dc.date.created | 2015-09-11 | - |
dc.date.created | 2015-09-11 | - |
dc.date.issued | 2007-04 | - |
dc.identifier.citation | INORGANIC CHEMISTRY, v.46, no.7, pp.2596 - 2603 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/10203/203335 | - |
dc.description.abstract | The manganese(III)-bis[poly(pyrazolyl)borate] complexes, Mn(pzb)(2)SbF6, where pzb(-) = tetrakis(pyrazolyl)borate (pzTp) (1), hydrotris(pyrazolyl)borate (Tp) (2), or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) (3), have been synthesized by oxidation of the corresponding Mn(pzb)(2) compounds with NOSbF6. The Mn(III) complexes are low-spin in solution and the solid state (mu(eff) = 2.9-3.8 mu(B)). X-ray crystallography confirms their uncommon low-spin character. The close conformity of mean Mn-N distances of 1.974(4), 1.984(5), and 1.996(4) angstrom in 1, 2, and 3, respectively, indicates absence of the characteristic Jahn-Teller distortion of a high-spin d(4) center. N-Mn-N bite angles of slightly less than 90(o) within the facially coordinated pzb(-) ligands produce a small trigonal distortion and effective D-3d symmetry in 1 and 2. These angles increase to 90.0(4)(o) in 3, yielding an almost perfectly octahedral disposition of N donors in Mn(Tp*)(2)(+). Examination of structural data from 23 metal-bis(pzb) complexes reveals systematic changes within the metal-(pyrazolyl)borate framework as the ligand is changed from pzTp to Tp to Tp*. These deformations consist of significant increases in M-N-N, N-B-N, and N-N-B angles and a minimal increase in Mn-N distance as a consequence of the steric demands of the 3-methyl groups. Less effective overlap of pyrazole lone pairs with metal atom orbitals resulting from the M-N-N angular displacement is suggested to contribute to the lower ligand field strength of Tp* complexes. Mn(pzb)(2)(+) complexes undergo electrochemical reduction and oxidation in CH3CN. The electrochemical rate constant (k(s,h)) for reduction of t(2g)(4) Mn(pzb)(2)(+) to t(2g)(3)e(g)(2) Mn(pzb)(2) (a coupled electron-transfer and spin-crossover reaction) is 1-2 orders of magnitude smaller than that for oxidation of t(2g)(4) Mn(pzb)(2)(+) to t(2g)(3) Mn(pzb)(2)(2+). k(s,h) values decrease as Tp* > pzTp > Tp for the Mn(pzb)(2)(+/0) electrode reactions, which contrasts with the behavior of the comparable Fe(pzb)(2)(+/0) and Co(pzb)(2)(+/0) couples. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | COUPLED ELECTRON-TRANSFER | - |
dc.subject | NMR CHEMICAL-SHIFTS | - |
dc.subject | CRYSTAL-STRUCTURES | - |
dc.subject | MANGANESE(III) COMPLEX | - |
dc.subject | MAGNETIC-PROPERTIES | - |
dc.subject | EXCHANGE REACTIONS | - |
dc.subject | LIGANDS | - |
dc.subject | CROSSOVER | - |
dc.subject | IRON(II) | - |
dc.subject | HEXACYANOMANGANATE(III) | - |
dc.title | Synthesis, structure, and properties of low-spin manganese(III)-poly(pyrazolyl)borate complexes | - |
dc.type | Article | - |
dc.identifier.wosid | 000245135900035 | - |
dc.identifier.scopusid | 2-s2.0-34247118280 | - |
dc.type.rims | ART | - |
dc.citation.volume | 46 | - |
dc.citation.issue | 7 | - |
dc.citation.beginningpage | 2596 | - |
dc.citation.endingpage | 2603 | - |
dc.citation.publicationname | INORGANIC CHEMISTRY | - |
dc.identifier.doi | 10.1021/ic062224+ | - |
dc.contributor.localauthor | Baik, Mu-Hyun | - |
dc.contributor.nonIdAuthor | Hossain, Ferdaus | - |
dc.contributor.nonIdAuthor | Rigsby, Matthew A. | - |
dc.contributor.nonIdAuthor | Duncan, Cole T. | - |
dc.contributor.nonIdAuthor | Milligan, Paul L., Jr. | - |
dc.contributor.nonIdAuthor | Lord, Richard L. | - |
dc.contributor.nonIdAuthor | Schultz, Franklin A. | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | COUPLED ELECTRON-TRANSFER | - |
dc.subject.keywordPlus | NMR CHEMICAL-SHIFTS | - |
dc.subject.keywordPlus | CRYSTAL-STRUCTURES | - |
dc.subject.keywordPlus | MANGANESE(III) COMPLEX | - |
dc.subject.keywordPlus | MAGNETIC-PROPERTIES | - |
dc.subject.keywordPlus | EXCHANGE REACTIONS | - |
dc.subject.keywordPlus | LIGANDS | - |
dc.subject.keywordPlus | CROSSOVER | - |
dc.subject.keywordPlus | IRON(II) | - |
dc.subject.keywordPlus | HEXACYANOMANGANATE(III) | - |
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