Organometallic chemistry in supercritical fluids. The generation and detection of dinitrogen and nonclassical dihydrogen complexes of Group 6, 7, and 8 transition metals at room temperature

Howdle, Steven M.; Healy, Michael A.; Poliakoff, Martyn

doi:10.1021/ja00168a027

Cited by 106 publications

(67 citation statements)

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“…Howdle et al (1989) synthesized 17,-C,H,Re(CO),-,(N,),, where x = l , 2, or 3, from the UV photolysis of $-C,H,Re(CO), in SC Xe doped with N,. The dinitrogen compound (x = 2) was stable at room temperature, In a subsequent report, Howdle et al (1990) extended their previous work by synthesizing (C, R,)M(CO),(N,) and (C, R,)M(CO),(H,) complexes [ M = Fe, Mn, Re, Cr; R = H for n = 4; R = H or Me for n = 5 or 61 from UV photolysis of a series of (C,R,)M(CO), compounds in SC Xe doped with H, or N,.…”

Section: Organometallic Reactionsmentioning

confidence: 93%

“…Poliakoffs group at the University of Nottingham has explored several organometallic systems in SCFs (Poliakoff et al, 1988(Poliakoff et al, , 1991Howdle et al, 1992). In one project, they started with metal carbonyls and photochemically replaced the CO with N, or H, (Howdle and Polaikoff, 1989;Howdle et al, 1989Howdle et al, , 1990. Performing these syntheses in SC Xe allowed high N, and H, concentrations in the reacting mixture, which facilitated the production and stabilization of previously unknown dinitrogen and dihydrogen complexes.…”

Section: Organometallic Reactionsmentioning

confidence: 99%

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Reactions at supercritical conditions: Applications and fundamentals

et al. 1995

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Section: Organometallic Reactionsmentioning

confidence: 93%

Section: Organometallic Reactionsmentioning

confidence: 99%

Reactions at supercritical conditions: Applications and fundamentals

et al. 1995

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“…Experiments in which (C 4 H 4 )Fe(CO) 3 was photolyzed in a highpressure IR cell in scXe under a N 2 pressure of 1200 psi showed that both N 2 complexes had been formed. 94 A similar experiment with H 2 in place of N 2 led to the formation of the nonclassical dihydrogen complex (C 4 H 4 )Fe(CO) 2 (H 2 ). This product is not very stable, decomposing under 1500 psi of H 2 at room temperature with a t 1/2 value of ∼10 min.…”

Section: After the Breakthrough Synthesis: Rapid Development Of Tmentioning

confidence: 94%

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

Seyferth

2002

Organometallics

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“…The table also shows that SCFs allow the multiple substitution of CO by N2 to occur [4,5,32]. This is perhaps one of the most intriguing features of this chemistry (Scheme 4.2-1).…”

Section: Chemistrymentioning

confidence: 90%

“…In SCFs, the exploration has mostly been done by IR [5,12,13], largely because it is experimentally simpler than NMR [14-191, ( Conventionally, exploratory experiments might be carried out in NMR tubes, with scale-up in Schlenk tubes.…”

Section: Synthesis Of Coordination Compoundsmentioning

confidence: 99%

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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Organometallic chemistry in supercritical fluids. The generation and detection of dinitrogen and nonclassical dihydrogen complexes of Group 6, 7, and 8 transition metals at room temperature

Cited by 106 publications

References 0 publications

Reactions at supercritical conditions: Applications and fundamentals

Reactions at supercritical conditions: Applications and fundamentals

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

Synthesis of Coordination Compounds

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