The synthesis of eight fluxional, diamagnetic group 4 complexes MR'(C₄H₆)[N(SiMe₂CH₂PR₂)₂] (M = Hf, Zr; R' = Ph, CH₂CMe₃; R = Me) and (M = Hf, Zr, R' = Cl; R = Me, CHMe₂ has been achieved. The X-ray crystallographic results of two of these complexes (M = Hf, Zr; R' = Ph; R = Me) indicate that the bonding of the diene unit has a significantly higher degree of ƞ⁴-π character than is present in Cp₂M(diene) (M = Hf, Zr) complexes, and therefore the M(II) resonance structure has more contribution to the overall bonding scheme. Consistent with all the NMR data available is that these complexes maintain a meridional coordination of the tridentate amide-phosphine ligand both in solution and in the solid state. The observed fluxional process is best described as diene rotation. Two of the diene complexes (M = Hf; R' = Cl; R = Me, CHMe₂ were found to react with allylmagnesium chloride and subsequently undergo a unique C-C bond forming reaction and rearrangement to generate two new non-fluxional diene complexes Hf [(ƞ⁴-CH₂CHCHCH)CH₂CH₂CH₂][N(SiMe₂CH₂PR₂)₂] (R = Me or CHMe₂). The latter of these two complexes has been crystallographically characterized. / Science, Faculty of / Chemistry, Department of / Graduate

Thesis (Ph. D.)--Ohio State University, 1940. / Includes bibliographical references (leaves 68-71). Available online via OhioLINK's ETD Center.

No description available.

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 126-127).

Thesis (Ph. D.)--Lehigh University, 2001. / Includes bibliographical references and vita.

No description available.

The behavior of biphenyl and naphthyl sulfinate and sulfoxylate esters under flash vacuum thermolytic and photolytic conditions was studied and a new tetrasubstituted dihydrophenanthrene was isolated. Several, 2,2'-biphenyl diols were synthesized including some with specifically deuterated alkyl chains. These diols were cyclized to give symmetrically substituted as well as cis-/trans- unsymmetrically substituted dibenzoxepins. The dynamic NMR properties of these dibenzoxepins were studied and the free energy barriers of conformational inversion were measured and related to the steric interactions of the alkyl substituents. The preferred conformations of the trans-dibenzoxepins were related to the relative stabilities of the alkyl substituents in the axial or equatorial position. The reaction of the 2,2'-biphenyl diols with trimethylsilylbromide yielded diolefinic biphenyls. In some other cases rearrangements to cyclized products were observed. The photolytic cyclization of the diolefinic biphenyls resulted in new tetrasubstituted tetrahydropyrenes and pyrenes.

Thesis--University of Florida. / Description based on print version record. Typescript. Vita. Bibliography: leaves 99-102.

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Diolefin metathesis, using a Re2O7 catalyst, failed to show a reactivity difference due to conjugation of double bonds. However, the same system allows reaction of pentadiene while not affecting cyclopentene yielding a successful reaction ΓÇô separation scheme for a piperylene concentrate mixture.