0000000001299058
AUTHOR
Michelle Faust
Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes
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 …
The Instability of Ni{N(SiMe3 )2 }2 : A Fifty Year Old Transition Metal Silylamide Mystery.
The characterization of the unstable Ni(II) bis(silylamide) Ni{N(SiMe3 )2 }2 (1), its THF complex Ni{N(SiMe3 )2 }2 (THF) (2), and the stable bis(pyridine) derivative trans-Ni{N(SiMe3 )2 }2 (py)2 (3), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric Ni(I) species, [Ni{N(SiMe3 )2 }]4 (4), also obtainable from LiN(SiMe3 )2 and NiCl2 (DME). Experimental and computational data indicate that the instability of 1 is likely due to ease of reduction of Ni(II) to Ni(I) and the stabilization of 4 through dispersion forces.
The Instability of Ni{N(SiMe3)2}2: A Fifty Year Old Transition Metal Silylamide Mystery
The characterization of the unstable NiII bis(silylamide) Ni{N(SiMe3)2}2 (1), its THF complex Ni{N(SiMe3)2}2(THF) (2), and the stable bis(pyridine) derivative trans-Ni{N(SiMe3)2}2(py)2 (3), is described. Both 1 and 2 decompose at ca. 25 °C to a tetrameric NiI species, [Ni{N(SiMe3)2}]4 (4), also obtainable from LiN(SiMe3)2 and NiCl2(DME). Experimental and computational data indicate that the instability of 1 is likely due to ease of reduction of NiII to NiI and the stabilization of 4 through dispersion forces. peerReviewed
CCDC 1401116: Experimental Crystal Structure Determination
Related Article: Michelle Faust, Aimee M. Bryan, Akseli Mansikkamäki, Petra Vasko, Marilyn M. Olmstead, Heikki M. Tuononen, Fernande Grandjean, Gary J. Long and Philip P. Power|2015|Angew.Chem.,Int.Ed.|54|12914|doi:10.1002/anie.201505518
CCDC 1401114: Experimental Crystal Structure Determination
Related Article: Michelle Faust, Aimee M. Bryan, Akseli Mansikkamäki, Petra Vasko, Marilyn M. Olmstead, Heikki M. Tuononen, Fernande Grandjean, Gary J. Long and Philip P. Power|2015|Angew.Chem.,Int.Ed.|54|12914|doi:10.1002/anie.201505518
CCDC 1555899: Experimental Crystal Structure Determination
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CCDC 1828738: Experimental Crystal Structure Determination
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CCDC 1555900: Experimental Crystal Structure Determination
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CCDC 1401113: Experimental Crystal Structure Determination
Related Article: Michelle Faust, Aimee M. Bryan, Akseli Mansikkamäki, Petra Vasko, Marilyn M. Olmstead, Heikki M. Tuononen, Fernande Grandjean, Gary J. Long and Philip P. Power|2015|Angew.Chem.,Int.Ed.|54|12914|doi:10.1002/anie.201505518
CCDC 1555898: Experimental Crystal Structure Determination
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CCDC 1555903: Experimental Crystal Structure Determination
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CCDC 1555901: Experimental Crystal Structure Determination
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CCDC 1555902: Experimental Crystal Structure Determination
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CCDC 1401115: Experimental Crystal Structure Determination
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CCDC 1555896: Experimental Crystal Structure Determination
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