Conformational preferences in six-coordinate, octahedral complexes of molybdenum(III). Synthesis and structure of MoX3(dppe)L [X = Cl, Br, I; dppe = bis(diphenylphosphino)ethane; L = tetrahydrofuran, acetonitrile, trimethylphosphine]

Owens, Beth E.; Poli, Rinaldo; Rheingold, Arnold L.

doi:10.1021/ic00307a008

Cited by 30 publications

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“…25,26 The NP3 Ph ligand was also reacted with both the bromide and the iodide precursor complexes, [MoX3(THF)3] X=Br, I, which have lower energetic barriers for the mer to fac halide rearrangement and therefore are more likely to encourage tridentate ligand coordination. 27 However, 31 P{ 1 H} NMR spectroscopic characterisation was similar to the chloride complex, with single resonances of the uncoordinated N-triphos arm observed at -66 and -58 ppm for 1-Br and 1-I respectively (figures S2 and S3). Attempts to also prepare 1 in non-coordinating solvents (toluene or DCM) to encourage facial chloride and tridentate N-triphos coordination were unsuccessful, resulting in decomposition products.…”

Section: Reaction Of the Np3mentioning

confidence: 81%

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

et al. 2018

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The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(iii) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

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Section: Reaction Of the Np3mentioning

confidence: 81%

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

et al. 2018

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“…The solvents were dried and freshly distilled under inert gas. The imidazolium salts PCP*HCl,28, 50 and the molybdenum precursors [MoCl 3 (thf) 3 ],51 [MoBr 3 (thf) 3 ],52 [MoI 3 (thf) 3 ],53 trans ‐[Mo(N 2 ) 2 (PPh 2 Me) 4 ] ( 1 ),35, 54 and [MoCl 3 (dpepp)]55 have been prepared using the literature procedure. IR spectra were recorded on a Bruker Alpha‐P ATR‐IR Spectrometer.…”

Section: Methodsmentioning

confidence: 99%

CaO‐Based CO₂ Sorbents: From Fundamentals to the Development of New, Highly Effective Materials

2013

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The enormous anthropogenic emission of the greenhouse gas CO2 is most likely the main reason for climate change. Considering the continuing and indeed growing utilisation of fossil fuels for electricity generation and transportation purposes, development and implementation of processes that avoid the associated emissions of CO2 are urgently needed. CO2 capture and storage, commonly termed CCS, would be a possible mid-term solution to reduce the emissions of CO2 into the atmosphere. However, the costs associated with the currently available CO2 capture technology, that is, amine scrubbing, are prohibitively high, thus making the development of new CO2 sorbents a highly important research challenge. Indeed, CaO, readily obtained through the calcination of naturally occurring limestone, has been proposed as an alternative CO2 sorbent that could substantially reduce the costs of CO2 capture. However, one of the major drawbacks of using CaO derived from natural sources is its rapidly decreasing CO2 uptake capacity with repeated carbonation-calcination reactions. Here, we review the current understanding of fundamental aspects of the cyclic carbonation-calcination reactions of CaO such as its reversibility and kinetics. Subsequently, recent attempts to develop synthetic, CaO-based sorbents that possess high and cyclically stable CO2 uptakes are presented.

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“…While the formation of mer ‐isomers for octahedral trihalide complexes is almost universally preferred, regardless of d‐electron count, treatment with PMe 3 converts mer ‐[MoI 3 (dppe)(THF)] into fac ‐[MoI 3 (dppe)(PMe 3 )]. The reasons seems to be steric since [MoI 3 (PMe 3 ) 3 ] is directly obtained from MoI 3 and PMe 3 as the mer ‐isomer . Reaction of mer ‐[MoI 3 (THF) 3 ] with Q + I – in THF produces crystalline Q[ trans‐ MoI 4 (THF) 2 ] (Q = Ph 4 P, Bu 4 N, Pr 4 N, PPN).…”

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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Conformational preferences in six-coordinate, octahedral complexes of molybdenum(III). Synthesis and structure of MoX3(dppe)L [X = Cl, Br, I; dppe = bis(diphenylphosphino)ethane; L = tetrahydrofuran, acetonitrile, trimethylphosphine]

Abstract: The ligand replacement reaction of the THF‐Mo(III) complexes (I) with the diphosphine (II) affords the mononuclear mer‐compounds (III).

Cited by 30 publications

References 0 publications

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

CaO‐Based CO₂ Sorbents: From Fundamentals to the Development of New, Highly Effective Materials

Molybdenum Iodides – from Obscurity to Bright Luminescence

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Conformational preferences in six-coordinate, octahedral complexes of molybdenum(III). Synthesis and structure of MoX3(dppe)L [X = Cl, Br, I; dppe = bis(diphenylphosphino)ethane; L = tetrahydrofuran, acetonitrile, trimethylphosphine]

Abstract: The ligand replacement reaction of the THF‐Mo(III) complexes (I) with the diphosphine (II) affords the mononuclear mer‐compounds (III).

Cited by 30 publications

References 0 publications

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

Synthesis and reactivity of an N-triphos Mo(0) dinitrogen complex

CaO‐Based CO2 Sorbents: From Fundamentals to the Development of New, Highly Effective Materials

Molybdenum Iodides – from Obscurity to Bright Luminescence

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CaO‐Based CO₂ Sorbents: From Fundamentals to the Development of New, Highly Effective Materials