The preparation and characterization of dimeric and tetrameric clusters of molybdenum and tungsten

dc.contributor.author Ryan, Timothy
dc.contributor.department Chemistry
dc.date 2018-08-16T19:58:27.000
dc.date.accessioned 2020-07-02T05:57:05Z
dc.date.available 2020-07-02T05:57:05Z
dc.date.copyright Thu Jan 01 00:00:00 UTC 1981
dc.date.issued 1981
dc.description.abstract <p>The cyclo-addition of two Mo(,2)Cl(,4)P(C(,6)H(,5))(,3)(,2)(CH(,3)OH)(,2) molecules has produced a new type of tetrameric molybdenum cluster, Mo(,4)Cl(,8)L(,4). Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo(,4)X(,8)L(,4) clusters where X = Cl, Br, I and L = PR(,3), P(SLASHCIRC)(,3), RCN, CH(,3)OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo(,4)Cl(,8)(PR(,3))(,4), R = C(,2)H(,5), n-C(,4)H(,9);The preparation of the analogous W(,4)Cl(,8)(PR(,3))(,4) cluster fromWCl(,4) was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species;The attempted preparation of a tetrameric tungsten cluster from W(,2)(mhp)(,4) was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W(,2)Cl(,2)(mhp)(,3), was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms was situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W(,2)('4+) dimer containing a quadruple metal-metal bond;('1)DOE Report IS-T-952. This work was performed under contractW-7405-eng-82 with the Department of Energy.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/6884/
dc.identifier.articleid 7883
dc.identifier.contextkey 6298537
dc.identifier.doi https://doi.org/10.31274/rtd-180813-12569
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/6884
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/79700
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/6884/r_8123129.pdf|||Sat Jan 15 01:29:51 UTC 2022
dc.subject.disciplines Inorganic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Inorganic chemistry
dc.title The preparation and characterization of dimeric and tetrameric clusters of molybdenum and tungsten
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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