Organometallic complexes dinitrogen complex

In summary, the tantalum hydride system adds to the few previously reported well-defined organometallic complexes capable of cleaving N-H bonds of ammonia to yield either an amido or an imido complex, and achieves unprecedented dinitrogen N=N triple bond cleavage with dihydrogen on isolated tantalum atoms to yield reduction of both N atoms. 

Although dinitrogen complexes such as [M(N2)2(dppe)2] are not strictly organometallic, they closely resemble the carbonyls described in Section II,C,6. This analogy as well as the discovery of the syntheses of organo-nitrogen compounds via electron-transfer reactions have led us to include a brief description of the most recent developments. 

One of the key advantages of supercritical solvents over conventional liquids is their unique combination of gas-like and liquid-like properties. Thus, reactant gases such as H2 or N2 can, under the correct conditions of temperature and pressure, be totally miscible with SCF solutions. At Nottingham, this unique property has been exploited to synthesize a range of novel organometallic complexes with metals bonded directly to dinitrogen [17] and dihydrogen [7,18], as shown in eq (3.1.1). These experiments are outlined in more detail in chapter 4.2. 

Semproni SP, Milsmann C, Chirik PJ. Side-on dinitrogen complexes of titanocenes with disubstituted cyclopentadienyl ligands synthesis, structure, and spectroscopic characterization. Organometallics. 2012 31 3672-3682. 

Hanna TE, Keresztes I, Lobkovsky E, Bemskoetter WH, Chirik PJ. Synthesis of a base-free titanium imido and a transient alkylidene from a titanocene dinitrogen complex. Studies on Ti = NR hydrogenation, nitrene group transfer, and comparison of 1,2-addition rates. Organometallics. 2004 23 3448-3458. 

Bernskoetter WH, Olmos AV, Lobkovsky E, Chirik PJ. N2 hydrogenation promoted by a side-on bound hafnocene dinitrogen complex. Organometallics. 2006 25 1021-1027. 

MacKay BA, Patrick BO, Fryzuk MD. Hydroalumination of a dinuclear tantalum dinitrogen complex N-N bond cleavage and ancillary Ugand rearrangement. Organometallics. 2005 24 3836-3841. 

Yuki M, Miyake Y, Nishibayashi Y, Wakiji I, Flidai M. Synthesis and reactivity of tungsten- and molybdenum-dinitrogen complexes bearing ferrocenyldiphosphines toward protonolysis. Organometallics. 2008 27 3947-3953. 

ManseU SM, Famaby JH, Germeroth AI, Arnold PL. ThermaUy stable uranium dinitrogen complex with sUoxide supporting Hgands. Organometallics. 2013 32 4214-4222. 

CHART 9 Selected examples of reduced dinitrogen organometallic rare earth complexes reported by Evans s group. 

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