Synthesis, structure, and properties of low-spin manganese(III)-poly(pyrazolyl)borate complexes

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dc.contributor.authorHossain, Ferdausko
dc.contributor.authorRigsby, Matthew A.ko
dc.contributor.authorDuncan, Cole T.ko
dc.contributor.authorMilligan, Paul L., Jr.ko
dc.contributor.authorLord, Richard L.ko
dc.contributor.authorBaik, Mu-Hyunko
dc.contributor.authorSchultz, Franklin A.ko
dc.date.accessioned2016-04-12T07:40:37Z-
dc.date.available2016-04-12T07:40:37Z-
dc.date.created2015-09-11-
dc.date.created2015-09-11-
dc.date.issued2007-04-
dc.identifier.citationINORGANIC CHEMISTRY, v.46, no.7, pp.2596 - 2603-
dc.identifier.issn0020-1669-
dc.identifier.urihttp://hdl.handle.net/10203/203335-
dc.description.abstractThe 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.languageEnglish-
dc.publisherAMER CHEMICAL SOC-
dc.subjectCOUPLED ELECTRON-TRANSFER-
dc.subjectNMR CHEMICAL-SHIFTS-
dc.subjectCRYSTAL-STRUCTURES-
dc.subjectMANGANESE(III) COMPLEX-
dc.subjectMAGNETIC-PROPERTIES-
dc.subjectEXCHANGE REACTIONS-
dc.subjectLIGANDS-
dc.subjectCROSSOVER-
dc.subjectIRON(II)-
dc.subjectHEXACYANOMANGANATE(III)-
dc.titleSynthesis, structure, and properties of low-spin manganese(III)-poly(pyrazolyl)borate complexes-
dc.typeArticle-
dc.identifier.wosid000245135900035-
dc.identifier.scopusid2-s2.0-34247118280-
dc.type.rimsART-
dc.citation.volume46-
dc.citation.issue7-
dc.citation.beginningpage2596-
dc.citation.endingpage2603-
dc.citation.publicationnameINORGANIC CHEMISTRY-
dc.identifier.doi10.1021/ic062224+-
dc.contributor.localauthorBaik, Mu-Hyun-
dc.contributor.nonIdAuthorHossain, Ferdaus-
dc.contributor.nonIdAuthorRigsby, Matthew A.-
dc.contributor.nonIdAuthorDuncan, Cole T.-
dc.contributor.nonIdAuthorMilligan, Paul L., Jr.-
dc.contributor.nonIdAuthorLord, Richard L.-
dc.contributor.nonIdAuthorSchultz, Franklin A.-
dc.type.journalArticleArticle-
dc.subject.keywordPlusCOUPLED ELECTRON-TRANSFER-
dc.subject.keywordPlusNMR CHEMICAL-SHIFTS-
dc.subject.keywordPlusCRYSTAL-STRUCTURES-
dc.subject.keywordPlusMANGANESE(III) COMPLEX-
dc.subject.keywordPlusMAGNETIC-PROPERTIES-
dc.subject.keywordPlusEXCHANGE REACTIONS-
dc.subject.keywordPlusLIGANDS-
dc.subject.keywordPlusCROSSOVER-
dc.subject.keywordPlusIRON(II)-
dc.subject.keywordPlusHEXACYANOMANGANATE(III)-
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