Although hydrides of metal carbonyls are widely known, the number of hydrides in the related family of metal nitrosyls is extremely small. The preparation of a series of nitrosyl hydrides from the treatment of [CpW(NO)I₂]₂ (Cp=ƞ⁵-C₅H₅) with Na[H₂Al(OCH₂CH₂OCH₃)₂] is described. The addition of one or two equivalents of the aluminum reagent results in the formation of [CpW(NO)IH]₂ or [CpW(NO)H₂]₂ respectively. The reaction of [CpW(NO)IH]₂ with a Lewis base (L=P(OPh)₃, P(OMe)₃, PPh₃ or PMe₃) gives the monometallic CpW(NO)IHL, while [CpW(NO)H₂]₂ reacts with P(OPh)₃ or P(OMe)₃ to yield [CpW(NO)HL]₂ which undergoes further reaction to give CpW(NO)H₂L. Proton NMR spectroscopy shows that all bimetallic species contain bridging hydride ligands and are therefore best, formulated as [CpW(NO)1]₂(µ-H)₂, [CpW(NO)H]₂(µ-H)₂ and [CpW(NO)L]₂(µ-H)₂.
The ¹H NMR spectrum of [CpW(NO)H]₂(µ-H)₂ shows that there is
no hydride ligand exchange on the NMR time scale and that
¹jH(terminal)W ≃ ¹jH(bridging)w > ²jHW. From this finding, it is
possible to develop new criteria for assessing the static or fluxional nature of hydride ligands for several families of organotungsten hydrides (Cp₂W, CpW(CO)₃, W(CO)₃ and CpW(NO)x (x=l or 2)). Within each family, the magnitude of ¹JHW strongly reflects the type of metal hydride bonding, i.e.
[Formula Omitted]
and suggests that bridge bonding involves all the atoms in the
bridge and therefore the "fused" notation is introduced.
Treatment of CpW(NO)(CH₂SiMe₃)₂ with low pressures of H₂
(60-80 psig) in the presence of Lewis bases (L=P(0Ph)₃, PMePh₂)
gives the unusually stable alkyl hydride compounds
CpW(NO)(H)(CH₂SiMe₃)L. This chemistry is then extended to the Cp* (Cp*=ƞ⁵ -C₅Me₅) analogues, including the preparation of the
appropriate starting materials. Upon thermolysis of
Cp*W(NO)(H)(CH₂SiMe₃)(PMe₃) in C₆H₆, the intermolecular C-H
activation product Cp*W(N0)(H)(C₆H₅)(PMe₃) is cleanly formed.
However, intermolecular activation of CH₄, C₆H₁₂ or n-C₆H₁₄ does
not occur under similar experimental conditions.
Hydrogenolysis of Cp*W(NO)(CH₂SiMe₃)₂ at high pressures (≃920 psig) with no Lewis base present results in the formation of isolable [Cp*W(NO)H]₂(µ-H)₂ and
[Cp*W(N0)H](µ-H)₂[Cp*W(N0)(CH₂SiMe₃)]. The latter is a new example of the rare class of dinuclear alkyl hydride complexes. Proton NMR spin tickling experiments on this compound allow the complete assignment of all couplings in the spectrum and show
that ¹jH(terminal)W' ¹JH(bridging)W and ²jHW have the same sign. / Science, Faculty of / Chemistry, Department of / Graduate
| Identifer | oai:union.ndltd.org:UBC/oai:circle.library.ubc.ca:2429/27449 |
| Date | January 1987 |
| Creators | Martin, Jeffrey Thomas |
| Publisher | University of British Columbia |
| Source Sets | University of British Columbia |
| Language | English |
| Detected Language | English |
| Type | Text, Thesis/Dissertation |
| Rights | For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use. |
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