Synthesis And Characterization Of Rutheniumii Phosphine Azide Complexes

Author : Jin Xie
Publisher : Open Dissertation Press
ISBN 13 : 9781361427293
Total Pages : pages
Book Rating : 4.4/5 (272 download)

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Download or read book Synthesis, Structures and Spectroscopic Properties of Primary and Secondary Phosphine Complexes of Iron, Ruthenium and Osmium Porphyrins written by Jin Xie and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Synthesis, Structures and Spectroscopic Properties of Primary and Secondary Phosphine Complexes of Iron, Ruthenium and Osmium Porphyrins" by Jin, Xie, 解錦, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled SYNTHESIS, STRUCTURES AND SPECTROSCOPIC PROPERTIES OF PRIMARY AND SECONDARY PHOSPHINE COMPLEXES OF IRON, RUTHENIUM AND OSMIUM PORPHYRINS Submitted by XIE JIN For the degree of Doctor of Philosophy at The University of Hong Kong in Oct 2007 Primary and secondary phosphine complexes of transition metals are of fundamental importance in metal-mediated P-H bond functionalization, phosphido/phosphinidene formation, and have applications in materials science. This thesis mainly describes the first isolation of primary and secondary phosphine complexes of a metalloporphyrin, along with their spectral, structural, and redox properties. The reactivity of primary and secondary phosphines coordinated to metalloporphyrins, particularly their hydrophosphination reactions with C=C bonds, is included. Investigations on the attempted approach to metal primary phosphine complexes bearing a pentapyridyl ligand (PY5) are also included. Ruthenium and osmium porphyrins form isolable complexes with primary and II secondary phosphines. Complexes [Ru (por)(PH Ph )] and n 3-n 2 II II [Os (por)(CO)(PH Ph )] (n = 1, 2) were prepared from reaction of [M (por)(CO)] n 3-n VI (M = Ru, Os) with excess PH Ph or PHPh . Reaction of [Os (por)O ] with PHPh 2 2 2 2 II mainly generated [Os (por){P(OH)Ph }(PHPh )], with concomitant formation of 2 2 II minor amounts of [Os (por){P(OH)Ph } ]. The bis-(primary phosphine) complex 2 2 II [Ru (F -tpp)(PH Ph)] is strikingly stable toward air and features reversible 20 2 2 +/0 Ru(II)/Ru(III) oxidation couple at E = 0.39 V vs Cp Fe . NMR spectrum 1/2 2 simulation revealed a strong coupling between the trans P nuclei in II 2 2 [Ru (por)(PH Ph ) ] (n = 1, 2; J ≈ 500 Hz). A J value of 467 Hz was directly n 3-n 2 PP PP 31 II obtained from the proton-decoupled P NMR spectrum of [Os (F - 20 tpp){P(OH)Ph }(PHPh )], which is much larger than that observed for the trans 2 2 phosphines in a non-porphyrin osmium phosphine complex. A one-pot synthesis of metal primary phosphine complexes from user-friendly O=PClR and PClR has been realized by treating these precursors with 2 2 II [Ru (por)(CO)] and LiAlH, leading to the isolation of primary alkylphosphine II complexes of ruthenium porphyrins, [Ru (por)(PH R) ] (por = ttp, 4-MeO-ttp, F -tpp; 2 2 20 t sec R = Ad, Bu, Bu), which are the first examples of primary alkylphosphine complexes of ruthenium. II Reactions of [Ru (F -tpp)(PH Ph ) ] (n = 1, 2) with CH =CHR (R = CO Et, 20 n 3-n 2 2 2 t II CN) in the presence of BuOK afforded [Ru (F -tpp){P(CH CH R) Ph } ] in high 20 2 2 n 3-n 2 yields. This is the first observation of alkene hydrophosphination by primary/secondary phosphines coordinated to a metalloporphyrin. The reactions of III [Fe (por)Cl] (por = F -tpp, 2,6-Cl tpp) with Na S O followed by treatment with 20 2 2 2 4 excess PH Ph, PHPh, or PH Ad led to the isolation of the first examples of iron 2 2 2 porphyrin complexes of primary and secondary phosphines, of which the primary phosphine complexes underwent partial dissociation in solutions at room temperature. Treatment of PY5 (or PY5-OH) with Ag(p-MeC H SO), AgNO, or 6 4 3 3 [Cu(MeCN) ]PF resulted in the isolation of [Ag (L) ]X (L = PY5 or PY5-OH, X = 4 6 2 2 2 - - I p-MeC H SO or NO ) and [Cu (PY5)(MeCN)]PF, which adopt two types of 6 4 3 3 6