Synthesis and Characterization of MoOI2(PMe3)3 and Use of MoOX2(PMe3)3 (X = Cl, I) in Controlled Radical Polymerization

Mata, José A.; Maria, Sébastien; Daran, Jean‐Claude; Poli, Rinaldo

doi:10.1002/ejic.200600156

Cited by 18 publications

(15 citation statements)

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“…This presumes that the ATRP process is taking place through Mo IV /Mo V -X redox couples. In this respect, we would like to point out that the Mo IV complexes MoOX 2 (PMe 3 ) 2 (X = Cl, I) have indeed been shown to efficiently catalyze the ATRP of styrene, yielding polymers with M n close to theory and quite low M w /M n [38]. As already mentioned above, our next investigations will aim at isolating the products of this oxidative addition process and to verify their ability to catalyze ATRP.…”

Section: A Verification Experimentsmentioning

confidence: 95%

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation using organometallic MoIII-based catalysts

Stoffelbach

Poli

Maria

et al. 2007

Journal of Organometallic Chemistry

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Compound CpMoI 2 (iPr 2 dad) (iPr 2 dad = iPrN@CHACH@NiPr), obtained by halide exchange from CpMoCl 2 (iPr 2 dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl 2 (iPr 2 dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irreversibly traps the corresponding growing radical chains under OMRP conditions. On the other hand, compound CpMoI 2 (iPr 2 dad) has a greater ATRP catalytic activity than the dichloro analogue and yields f = 1 for MA and ethyl 2-iodopropionate as initiator. Under OMRP conditions, it does not irreversibly trap the growing radical chains. This comparison serves to illustrate the general principle that low initiator efficiency factors, sometimes observed in ATRP, may result from the interplay of the ATRP and OMRP mechanisms, when the latter ones involves an irreversible radical trapping process.

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Section: A Verification Experimentsmentioning

confidence: 95%

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation using organometallic MoIII-based catalysts

Stoffelbach

Poli

Maria

et al. 2007

Journal of Organometallic Chemistry

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“…The iodide in [MoOI 2 (PMe 3 ) 3 ] is completely replaced by chloride in CHCl 3 , and by bromide in 1‐bromoethylbenzene. The iodide complex catalyzes atom transfer radical polymerization of styrene, yielding polymers with narrow molecular weight distribution . [MoOI 2 (PMe 3 ) 3 ] was further converted, by treatment with a tetradentate phosphane ligand, 1,1,4,8,11,11‐hexaphenyl 1,4,8,11‐tetraphosphaundecane (prP 4 ), and NaBPh 4 , into [MoOI(prP 4 )](BPh 4 ), which was then electrolytically reduced at – 2.1 V (vs. Ag electrode) under N 2 in THF to give trans ‐[Mo(N 2 ) 2 (prP 4 )] .…”

Section: Low Nuclearity Complexes and Clustersmentioning

confidence: 99%

Molybdenum Iodides – from Obscurity to Bright Luminescence

Mikhaylov

Sokolov

2019

Eur J Inorg Chem

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This review is dedicated to the chemistry of Mo iodides. These compounds have a humble origin, and for a long time their chemistry has been almost completely neglected. Although important work on mononuclear and dinuclear Mo iodide complexes was done in 1980-1990s, the situation has dramatically changed within the last decade. The finding that the IntroductionThe iodides of transition metals attract much less attention than their chloride and bromide analogues, even though a book dealing exclusively with metal iodides was published half a century ago. [1] This is partly explainable by general lack of current or proposed practical use for this class of compounds. A notable exception offer the volatile iodides of Ti, Zr, and Hf, and of a few other metals, that can be used in the iodide process of van Arkel and de Boer. [2] Among the group 6 metals, this process can be applied for preparation of high purity chromium, which [a] Nikolaev His research interests focus on the coordination chemistry of 4d and 5d transition metals. Maxim Mikhaylov was born in Novosibirsk, (Russia). In 2009-2013 he completed his Ph. D. at the Laboratory of cluster and supramolecular compounds in the Nikolaev Institute of Inorganic Chemistry (NIIC) under suporevision of Prof. Dr. M. N. Sokolov. Now he is a researcher working in the Laboratory of synthesis of cooridnation compounds at NIIC. His research interests include synthesis of novel clusters and cluster complexes for the development of new materials.

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“…In order to make the Mo IV oxido precursor more reactive towards the coordination of prP 4 , the chloro ligands of 1 were subsequently exchanged for iodides, leading to the complex mer ‐ cis [Mo(O)I 2 (PMe 3 ) 3 ] ( 2 ) which had been prepared and characterized by Poli et al recently (Scheme , center) 13. Like its chloro congener, 2 exhibits an AX 2 coupling Scheme in the 31 P NMR spectrum, this time with a J AX coupling constant of –22.7 Hz.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand

et al. 2008

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The first Chatt‐type Mo0 dinitrogen complex with a tetraphosphane ligand has been prepared and characterized by NMR as well as infrared and Raman spectroscopy. Importantly, the employed reaction route allows the stereospecific synthesis of this complex as trans‐[Mo(N2)2(meso‐prP4)] (prP4 = a tetraphos ligand with a central propylene bridge). The stereoselectivity in the reaction course is induced by the oxido‐iodido‐molybdenum(IV) precursor [Mo(O)I(prP4)]+ which directs both phenyl groups of the bridging P atoms of prP4 into a meso configuration. The paper establishes a general strategy to synthesize mononuclear Mo0 dinitrogen and related molybdenum complexes with multidentate phosphane ligands which has not been possible to date. Moreover, the obtained molybdenum tetraphos N2 complex should exhibit a higher thermodynamic stability in the reactions of the Chatt cycle of synthetic nitrogen fixation than the conventional bis(diphos) complexes, due to the linkage of the two diphosphane units by an alkyl bridge. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Synthesis and Characterization of MoOI₂(PMe₃)₃ and Use of MoOX₂(PMe₃)₃ (X = Cl, I) in Controlled Radical Polymerization

Cited by 18 publications

References 29 publications

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation using organometallic MoIII-based catalysts

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation using organometallic MoIII-based catalysts

Molybdenum Iodides – from Obscurity to Bright Luminescence

Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand

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