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UBC Theses and Dissertations

New organomtallic nitrosyl derivatives of the group 6B elements Martin, David Timothy


The complexes CpM(NO)₂Cl (M=Cr, Mo or W) can be reduced using Na[A1H₂(OCH₂CH₂OCH₃)₂] to yield [CpCr(NO)₂]₂ and CpM(NO)₂H (M=Mo or W), respectively. A study of the chemistry of CpW(NO)₂H shows that it acts as a source of the hydride ion in polar solvents. For example, CpW(NO)₂H reacts with anhydrous p-toluenesulfonic acid to form CpW(NO)₂S0₃-C₇H₇. The complex also undergoes loss of H⁻ with Ph3CBF₄. This novel reactivity is compared with that exhibited by carbonylhydride complexes of the transition metals. The molybdenum congener, CpMo(NO)₂H, is unstable in the solid state but can be characterized in solution. No direct physical evidence can be found for the existence of CpCr(NO)₂H. The reaction of I₂ with CpW(CO)₂NO results in the isolation of a completely decarbonylated product, [CpW(NO)I₂]₂. CpW(CO)₂NO + I₂ → 1/2[CpW(NO)I ]₂ This dimeric compound reacts with a variety of reagents to form monomeric products. [FORMULA OMMITTED] An X-ray crystallographic analysis of this complex shows that the allyl group exhibits considerable σ π, ir distortion. This asymmetry is also evident in solution at ambient temperature. This fact allows straightforward analysis of the ¹H and ¹³C magnetic resonance spectra. The previously reported molybdenum analogue, [FORMULA OMMITTED] can be prepared by allylation of [FORMULA OMMITTED]

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