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Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes.
Pratt, Jade; Bryan, Aimee M; Faust, Michelle; Boynton, Jessica N; Vasko, Petra; Rekken, Brian D; Mansikkamäki, Akseli; Fettinger, James C; Tuononen, Heikki M; Power, Philip P.
Afiliação
  • Pratt J; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Bryan AM; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Faust M; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Boynton JN; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Vasko P; Department of Chemistry, Nanoscience Center , University of Jyväskylä , P.O. Box 35, FI-40014 Jyväskylä , Finland.
  • Rekken BD; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Mansikkamäki A; Department of Chemistry, Nanoscience Center , University of Jyväskylä , P.O. Box 35, FI-40014 Jyväskylä , Finland.
  • Fettinger JC; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
  • Tuononen HM; Department of Chemistry, Nanoscience Center , University of Jyväskylä , P.O. Box 35, FI-40014 Jyväskylä , Finland.
  • Power PP; Department of Chemistry , University of California , One Shields Avenue , Davis , California 95616 , United States.
Inorg Chem ; 57(11): 6491-6502, 2018 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-29745653
ABSTRACT
The first-row transition-metal(II) dithiolates M(SAriPr4)2 [AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2; M = Cr (1), Mn (3), Fe (4), Co (5), Ni (6), and Zn (7)] and Cr(SArMe6)2 [2; ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2] and the ligand-transfer reagent (NaSAriPr4)2 (8) are described. In contrast to their M(SAriPr6)2 (M = Cr, Mn, Fe, Co, Ni, and Zn; AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2) congeners, which differ from 1 and 3-6 in having p-isopropyl groups on the flanking aryl rings of the terphenyl substituents, compounds 1 and 4-6 display highly bent coordination geometries with S-M-S angles of 109.802(2)° (1), 120.2828(3)° (4), 91.730(3)° (5), and 92.68(2)° (6) as well as relatively close metal-flanking aryl ring η6 interactions with metal-centroid distances of 2.11477(6) Å (1), 1.97188(3) Å (2), 2.15269(6) Å (4), 1.62058(9) Å (5), and 1.724(8) Å (6). However, the d5 (Mn) and d10 (Zn) complexes 3 and 7 display linear or near-linear coordination with no close metal-ligand distances. The nonlinear geometries of 1 and 4-6 also contrast with those of their AriPr4-substituted alkoxo and amido congeners, which have strictly linear coordination. Complexes 1-7 were synthesized by the reaction of the lithium or sodium thiolate salt with the metal dihalide or, in the case of 3, by the reaction of the thiol with the amido complex Mn[N(SiMe3)2]2. All compounds were characterized by electronic spectroscopy, X-ray crystallography, and magnetic measurements using Evans' method and SQUID magnetometry. It was concluded that, despite the large bulk of the AriPr4 substituents, the absence of p-isopropyl groups on the flanking rings of the ligand permits close secondary metal-flanking ring distances. The compounds are characterized by more intense colors and display magnetic moments that are generally lower than the spin-only values, in agreement with the covalent character of the close metal-flanking ring η6 interactions.

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Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: Inorg Chem Ano de publicação: 2018 Tipo de documento: Artigo País de afiliação: Estados Unidos