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Chapter 1. The chemistry of the metal-metal multiply bonded Tc2(II, II) core has been investigated with bis(diphenylphosphino)methane (dppm). The parent complex, Tc2Cl4(dppm)2, has been prepared from the reaction of Tc2C14(PEt3)4 with dppm. The reactivity of Tc2Cl4(dppm)2 with tert-butyl isocyanide has been studied and a neutral 1:1 adduct, Tc2Cl4(dppm)2CNBut, a cationic 1:2 adduct, [Tc2Cl3(dppm)4(CNBut)2](PF6), and a [mu]-iminyl complex, [Tc2Cl3(dppm)2(CNBut)2CNHBul(PF6), have been prepared. The parent compound and its reaction products have been characterized via a combination of spectroscopic techniques and single crystal X-ray crystallography. The metal-metal bonded ditechnetium bis(dppm) motif is retained in the reaction products. Chapter 2. The reduction of ammonium pertechnetate with bis(diphenylphosphino)methane (dppm), and with diphenyl-2-pyridyl phosphine (Ph2Ppy), has been investigated. The neutral Tc(II) complex, TcCl2(dppm)2, has been isolated from the reaction of (NH4)[TcO4] with excess dppm in refluxing EtOH/HCl. Chemical oxidation with ferricinium hexafluorophosphate results in formation of the cationic Tc(III) analogue, [TcCl2(dppm)2](PF6). The dppm ligands adopt the chelating bonding mode in both complexes, resulting in strained four member metallocycles. With excess PhPpy, the reduction of (NH4)[TcO4] in refluxing EtOH/HCl yields a complex with one chelating Ph2Ppy ligand and one unidentate Ph2Ppy ligand, TcCl3(Ph2Ppy-P, N)(Ph2Ppy-P).
Investigations of ligands capable of donating/accepting hydrogen bonds in important catalytic applications were undertaken. It has been found that heterocyclic phosphine ligands, namely 2-pyridyl and 2-imidazolyl phosphines, greatly influence the reactivity of CpRu catalysts. This has led to highly efficient anti-Markovnikov hydration of a variety of terminal alkynes, including aryl alkynes and trimethylsilyl alkynes. Enzyme-like rate enhancements of>109 have facilitated experimental and computational mechanistic studies, supporting multipoint cooperativity involving the metal and the heterocyclic phosphine ligands.
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