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The Butterfly Dimer [(<sup>t</sup>Bu<sub>3</sub>SiO)Cr]<sub>2</sub>(μ-OSi<sup>t</sup>Bu<sub>3</sub>)<sub>2</sub> and Its Oxidative Cleavage to (<sup>t</sup>Bu<sub>3</sub>SiO)<sub>2</sub>Cr(N−NCPh<sub>2</sub>)<sub>2</sub> and (<sup>t</sup>Bu<sub>3</sub>SiO)<sub>2</sub>CrN(2,6-Ph<sub>2</sub>-C<sub>6</sub>H<sub>3</sub>)
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Citations
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References
2006
Year
Inorganic ChemistryX-ray Structural StudiesEngineeringMolecule-based MagnetBiochemistryNatural SciencesBoltzmann DistributionMagnetic ResonanceMolecular BiologySquare PlanarStructure ElucidationOxidative CleavageChemistryCrystallographyInorganic SynthesisInorganic Compound
Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 (1(2)), whose d(CrCr) of 2.658(31) A 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(muOH)2 (1'(2)) were used to provide a reasonable fit of the mu(eff) 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 degrees 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 pseudo-trigonal 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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