The Butterfly Dimer [(tBu3SiO)Cr]2 (μ-OSitBu3)2 and Its Oxidative Cleavage to (tBu3SiO)2 Cr(=N-N=CPh2)2 and (tBu3SiO)2 Cr=N(2,6-Ph2-C6H3)

Description:

Article discussing research on the butterfly dimer [(ᵗBu₃SiO)Cr]₂(μ-OSiᵗBu₃)₂ and its oxidative cleavage to (ᵗBu₃SiO)₂Cr(=N-N=CPh₂)₂ and (ᵗBu₃SiO)₂Cr=N(2,6-Ph₂-C₆H₃).

Creator(s):
Creation Date: January 12, 2006
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Creator (Author):
Sydora, Orson L.

Cornell University

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Kuiper, David S.

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Creator (Author):
Wolczanski, Peter T.

Cornell University

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Lobkovsky, Emil B.

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Dinescu, Adriana

University of North Texas

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Cundari, Thomas R., 1964-

University of North Texas

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: January 12, 2006
Description:

Article discussing research on the butterfly dimer [(ᵗBu₃SiO)Cr]₂(μ-OSiᵗBu₃)₂ and its oxidative cleavage to (ᵗBu₃SiO)₂Cr(=N-N=CPh₂)₂ and (ᵗBu₃SiO)₂Cr=N(2,6-Ph₂-C₆H₃).

Degree:
Department: Chemistry
Note:

Reprinted with permission from Inorganic Chemistry. Copyright 2006 American Chemical Society.

Note:

Abstract: Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the butterfly dimer [(tBu3SiO)Cr]2 (μ-OSitBu3)2 (1 2), whose d(CrCr) of 2.658(31) Å and magnetism were indicative of strong antiferromagnetic coupling. A Boltzmann distribution of low-energy 1A1, 3B1, 5A1, 7B1, and 9A1 states obtained from calculations on [(HO)2Cr]2(μOH)2 (1'2) were used to provide a reasonable fit of the μeff vs T data. Cleavage of 1 2 with various L (L=4-picoline, p-tolunitrile, tBuCN, tBuNC, Ph2CO, and PMe3) generated (tBu3SiO)2CrL2(1-L2). The dimer was oxidatively severed by Ph2CN2 to give (tBu3SiO)2Cr(N2CPh2)2 (2) and by RN3 at 23 ˚C to afford (silox)2Cr=NR (3-R) for bulky R (adamantyl (Ad), 2,6-iPr2-C6H3, 2,4,6-Me3-C6H2 = Mes, 2,6-Ph2-C6H3) and (tBu3SiO)2Cr(=NR)2 (4-R) for smaller substituents (R = 1-Naph, 2-Anth). X-ray structural studies were conducted on 1 2, square planar 1-(OCPh2)2, pseudo-Td 2 and pseudotrigonal 3-(2,6-Ph2-C6H3), whose S = 1 ground state was discussed on the basis of calculations of (H3SiO)2Cr = NPh (3"-Ph).

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14 p.

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Subject(s):
Keyword(s): butterfly dimers | oxidative cleavage
Source: Inorganic Chemistry, 2006, Washington DC: American Chemical Society, pp. 2008-2021
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ic051481w |
  • ARK: ark:/67531/metadc75425
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Inorganic Chemistry
Volume: 45
Issue: 5
Page Start: 2008
Page End: 2021
Pages: 14
Peer Reviewed: Yes