Flow Reactors for Preparative Chemistry in Supercritical Fluid Solution: "Solvent-Free" Synthesis and Isolation of Cr(CO)5(C2H4) and (.eta.5-C5H5)Mn(CO)2(.eta.2-H2)

Banister, James A.; Lee, Peter; Poliakoff, Martyn

doi:10.1021/om00008a039

Cited by 64 publications

(71 citation statements)

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“…3000 cm-') due to the v(H-H) vibration of the q2-H2 ligand [26,27]. These deductions were fully supported in those cases [6,7] where the compounds were finally isolated and characterized by 'H NMR. Therefore, there has been no success in observing the v(H-H) bands of any of the compounds listed in the table.…”

Section: Chemistrymentioning

confidence: 63%

“…The high concentration of gases has, in turn, led to the photochemical generation of a whole range of previously unknown dihydrogen and dinitrogen complexes [3-51, some of which have been isolated by the procedures outlined below [6,7]. Indeed, all of the syntheses described below involve a photochemical step, either in SCF solution or immediately prior to the use of the SCF.…”

Section: Strategymentioning

confidence: 99%

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Synthesis of Coordination Compounds

King¹,

Poliakoff²

1999

Chemical Synthesis Using Supercritical Fluids

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Historically, interest in supercritical fluids (SCFs) has been cyclical or, perhaps more accurately, sinusoidal. Currently, research into SCFs is undergoing a substantial resurgence, largely driven by possible applications in so-called "green" chemistry, where supercritical C02 (scCO2) offers considerable scope as an environmentally more acceptable replacement for conventional organic solvents. However, the emphasis here is rather different because the synthesis of new organometallic or coordination compounds in SCFs does not have such obviously. green applications as homogeneous catalysis (see chapter 4.7). Nevertheless, these compounds occupy an important place in SCF chemistry because they represent a large number of the new compounds which have been prepared in SCF solution.The use of coordination compounds in SCFs is rather larger than one might initially expect [I]. The major applications can be divided into two broad categories: (1) the transport of metals, which includes selective extraction, deposition of metal and oxide films and impregnation of metals as a route to composite materials; and (2) synthesis and reactions, which covers a wide range of topics from the synthesis of oxides and other solid state materials to the reactions of organometallic compounds. This chapter focuses on the synthesis of organometallic compounds because this is the area where the majority of the new experimental techniques have been developed. The chapter complements chapter 3.1 and 3.2 which cover, respectively, vibrational and NMR spectroscopy, because IR spectroscopy, and to a lesser extent NMR, have been key tools in the exploration of this chemistry.The chapter is divided into four parts: Strategy, which explains the rationale for carrying out these reactions in SCF solution; Chemistry, which outlines what the reactions are; Equipment, which describes some of the key components and introduces a modular approach to high pressure experiments; and Synthesis, which gives details of how to make particular compounds, including the use of flow reactors and semiflow reactors. It concludes with a brief summary and outlook.

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Section: Chemistrymentioning

confidence: 63%

Section: Strategymentioning

confidence: 99%

Synthesis of Coordination Compounds

King¹,

Poliakoff²

1999

Chemical Synthesis Using Supercritical Fluids

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“…One such complex initially presumed to be unstable, CpMn(H 2 )(CO) 2 , was in fact isolated as a solid from supercritical CO 2 (scCO 2 ) at room temperature in a flow reactor by rapid expansion of the scCO 2 (Scheme 5.21). 163,164 This complex is more robust than originally thought: displacement of the h 2 -H 2 by N 2 (500 psi) or ethylene requires 2 h in supercritical CO 2 . CpMn(H 2 )(CO) 2 is one of the simplest stable H 2 complexes and has the lowest molecular weight (178) and highest percentage of H 2 by weight (1.1%) of any isolatable transition metal H 2 complex.…”

Section: Vibrational Spectroscopy Of Unstable Dihydrogen Complexesmentioning

confidence: 97%

“…131,[160][161][162][163][164] In all media, vibrational spectroscopy provided the crucial evidence for H 2 rather than dihydride binding. The H--H, H--D, and D--D stretching modes are often observed because of the clear spectroscopic window in rare-gas media, although the experiments are decidedly much more difficult than routine IR or Raman spectroscopy.…”

Section: Vibrational Spectroscopy Of Unstable Dihydrogen Complexesmentioning

confidence: 99%

Activation of Molecular Hydrogen

Kubas

Heinekey

2010

Physical Inorganic Chemistry

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“…Alkene complexes of transition metals [18][19][20][21][22][23][24] play an important role in understanding the reaction mechanisms for hydrogenation of alkenes, which has been confirmed experimentally and theoretically to proceed via a wide variety of different pathways [25][26][27][28][29][30]. Rhodium (I) complexes with bidentate b-diketonato ligands are well-known catalysts for hydrogenation of alkene and are also used for hydroformylation of olefin [31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%