Computational Study Of Small Molecule Activation Via Low Coordinate Late First Row Transition Metal Complexes

Author : Aimee M. Bryan
Publisher :
ISBN 13 : 9781321608106
Total Pages : pages
Book Rating : 4.6/5 (81 download)

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Download or read book Synthesis and Characterization of Low Coordinate Transition Metal Complexes written by Aimee M. Bryan and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation describes the synthesis, characterization, and reactivity studies of new low-coordinate complexes of readily available and inexpensive transition metals such as iron, cobalt and nickel. The compounds were magnetically characterized in detail and tested for single molecule magnet (SMM) behavior. SMMs are a topic of intense research because of their potential applications in magnetic memory, high-density information storage and quantum computing technologies. Low-coordinate compounds display magnetic moments that indicate high orbital angular momentum and are very promising candidates for SMM behavior because they also tend to have large negative zero-field splitting (D) values. The complexes reported here are stabilized by using a variety of amido, aryloxo and thiolato ligands with bulky terphenyl groups and also using aryl and alkyl substituted silylamides. A superconducting quantum interference device (SQUID) and Evans' methods were used to study the magnetic properties and single crystal X-ray crystallography and NMR (1H and 13C) were used to confirm the structures of these compounds in both the solid and solution states. Further characterization studies included UV-visible, near-IR, and IR spectroscopy, melting point, elemental analysis and DFT calculations, where applicable, in order to determine the electronic configurations and bonding schemes. At present there are ca. 100 stable open shell two-coordinate mononuclear transition metal complexes currently known but ca. 20% have a linear coordination at the metal atom with only a few being strictly 180° at their metal center. Very few of these compounds had been magnetically characterized. In Chapter 2, the synthesis and magnetic characterization of the late transition metal Co2+ (d7) and Ni2+ (d8) primary amido complexes Co{N(H)Ar(iPr6)}2, Co{N(H)Ar(Me6)}2, Ni{N(H)Ar(iPr6)}2 and Ni{N(H)Ar(Me6)}2 (Ar(Me6) = C6H3-2,6(C6H2-2,4,6-Me3)2, Ar(iPr6) = C6H3-2,6(C6H2-2,4,6-(i)Pr3)2) are described. The investigations showed that they exhibit interesting magnetic behavior. The bent versus linear geometries of the complexes enable direct observation of the effects of orbital angular momentum quenching upon bending the metal coordination geometry. The electronic configuration of the linear cobalt(II) complexes does not predict first order orbital angular momentum and yet, the magnetic moment of Co{N(H)Ar(iPr6))2 is much higher than the spin only value which suggests a large spin-orbit coupling effects due to mixing of the ground and excited states. In Chapter 3, the synthesis and characterization of the mononuclear chromium, iron, cobalt and nickel terphenyl substituted thiolate complexes Cr(SAr(Me6))2, Cr(SAr(iPr4))2, Fe(SAr(iPr4))2, Co(SAr(iPr4))2 and Ni(SAr(iPr4))2 are described. Their structures show bent coordination geometries of varying degree with strong secondary M-[eta]6 and M-C(ipso) flanking aryl ring interactions of ca. 2.153 [Angstrom] for Fe(SAr(iPr4))2, ca. 1.625 [Angstrom] for Co(SAr(iPr4))2 and ca. 1.731 [Angstrom] for Ni(SAr(iPr4))2. This observation is in sharp contrast to the almost linear coordination observed for the derivatives of the related but more crowded terphenyl thiolate ligand, SAr(iPr6), in M(SAr(iPr6))2 complexes where M = Cr, Fe, Co and Ni and the strictly linear geometry observed for the terphenyloxo analogs M(OAr(iPr4))2 where M = Fe and Co. Magnetic moments for these species are, in general, lower than the spin-only values. Expect for chromium, this is an unexpected observation for late transition metal low-coordinate complexes. The suppression of magnetic moments is most like due to the strong M-arene interactions which effectively increases the coordination number at the metal atom. These results demonstrate the important role that substituents play on the flanking rings of the terphenyl ligands and begs further investigations involving the role of dispersion in the isolation of low coordination mononuclear transition metal complexes. The divalent silylamides M{N(SiMe3)2}2 (M = Mn, Fe, and Co) are key synthons for low-coordinate transition-metal derivatives. In Chapter 4, the previously reported, but incorrectly characterized cobalt(II) silylamide, [Co{N(SiMe3)2}2]2 has been spectroscopically and magnetically characterized for the first time. In addition, the new Lewis base complexes [Co{N(SiMe3)2}2(PMe3)], and [Co{N(SiMe3)2}2(THF)], as well as a previously reported complex [Co{N(SiMe3)2}2(py)] were isolated and characterized. Magnetic studies showed that they had considerably larger magnetic moments than the spin-only value of 3.87 [mu](B), which is indicative of a significant zero-field splitting and g-tensor anisotropy. In addition to their interesting magnetic behavior and unexpectedly large D values in the range of -20 to -80 cm−1. The electronic spectrum of [Co{N(SiMe3)2}2]2 in solution showed that earlier characterization spectra of "Co{N(SiMe3)2}2" match that of the bright green THF adduct and not the dark brown cobalt dimer [Co{N(SiMe3)2}2]2. In Chapter 5, it is shown that the reaction of the versatile cobalt(II) amide, [Co{N(SiMe3)2}2]2, with four equivalents of the sterically crowded terphenyl phenols, HOAr(Me6) and HOAr(iPr4) (Ar(iPr4) = C6H3-2,6(C6H3-2,6-(i)Pr2)2) produced the first well-characterized, monomeric two-coordinate cobalt(II) bisaryloxides, Co{OAr(Me6))2 and Co(OAr(iPr4))2. Not only are these very rare examples of two-coordinate transition metal(II) aryloxides, but the magnetic moments of both the linear and the bent species were well in excess of the spin only value for cobalt(II) ion. It was demonstrated that careful manipulation of the synthetic conditions for Co(OAr(iPr4))2 could produce varying occupancies of the cobalt(II) site and that after weighting the magnetic susceptibilities of the compounds accordingly, the moments were shown to be in close agreement with each other. Chapter 6 reports the synthesis of the unstable nickel(II) bis(silylamide) complex Ni{N(SiMe3)2}2 via the reaction of NiI2 and two equivalents of NaN(SiMe3)2 in tetrahydrofuran, as well as two of its Lewis base adducts, Ni{N(SiMe3)2}2(THF) and Ni{N(SiMe3)2}2(py)2. The reaction of two equivalents of LiN(SiMe3)2 with NiCl2(DME) in tetrahydrofuran afforded the reduced homoleptic tetrameric nickel(I) amide complex, [Ni{N(SiMe3)2}]4. This unique polymetallic structure having a Ni4N4 planar array has four S = 1/2 nickel (I) ions and an antiferromagnetic exchange coupling constant of J = -102(2) cm−1. This study provides strong evidence that the formation of nickel(II) and nickel(I) amido complexes is possible without the use of sterically demanding ligand sets.