Ligand-assisted reduction of Co(II) to Co(I) and subsequent coordination of dinitrogen

2005 ◽  
Vol 83 (4) ◽  
pp. 279-285 ◽  
Author(s):  
Jennifer Scott ◽  
Sandro Gambarotta ◽  
Ilia Korobkov
Keyword(s):  
Key Words ◽  
Bond Formation ◽  
Nitrogen Atmosphere ◽  
Dinitrogen Fixation ◽  
Dinuclear Complex ◽  
Methylene Carbon ◽  
Low Valent ◽  
Dinitrogen Complex ◽  
Identical Unit

Reaction of the bis-aminopyridine dianion {[2,6-[2,6-(i-Pr)2PhN-C=(CH2)]2(C5H3N)]Li(THF)}{Li(THF)4} with CoCl2(THF)1.5 under Ar afforded the dinuclear complex {[2,6-(i-Pr)2PhN-C=(CH2)](C5H3N)[2,6-(i-Pr)2PhN=C(CH2)]}2[Co(µ-Cl)Li(THF)3]2·4(THF) (1) in which the ligand is coupled to a second identical unit at a terminal methylene carbon. In turn, the C—C bond formation caused reduction of the Co(II) center to the monovalent state. The same reaction performed under a nitrogen atmosphere afforded the double dinitrogen complex {[2,6-(i-Pr)2PhN-C=(CH2)](C5H3N)[2,6-(i-Pr)2PhN=C(CH2)]}2[Co(N2)]2·2(toluene) (2). Key words: low-valent Co, diiminopyridinato, dinitrogen fixation.

scholarly journals Low-Valent Pentafulvene Titanium Dinitrogen Complex as a Precursor for Cationic Titanium Complexes

2009 ◽  
Vol 28 (24) ◽  
pp. 6969-6974 ◽  
Author(s):  
Axel Scherer ◽  
Detlev Haase ◽  
Wolfgang Saak ◽  
Rüdiger Beckhaus ◽  
Auke Meetsma ◽  
...  
Keyword(s):  
Titanium Complexes ◽  
Low Valent ◽  
Dinitrogen Complex

Synthesis and structure of a terminal dinitrogen complex of nickel

2005 ◽  
Vol 83 (4) ◽  
pp. 328-331 ◽  
Author(s):  
Rory Waterman ◽  
Gregory L Hillhouse
Keyword(s):  
Crystal Structure ◽  
Petroleum Ether ◽  
Key Words ◽  
X Ray ◽  
Dinitrogen Complex

Reaction of petroleum ether solutions of [(dtbpe)Ni]2(η2,µ-C6H6) (1, dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) with triphenylphosphine under a dinitrogen atmosphere gives the Ni(0) dinitrogen adduct (dtbpe)Ni(N2)(PPh3) (2), which can be isolated as dark red crystals in 87% yield. The X-ray crystal structure of 2 reveals pseudotetrahedral geometry about Ni and a terminal dinitrogen ligand with Ni—N(1) = 1.830(2) Å, N(1)—N(2) = 1.112(2) Å, and Ni-N(1)-N(2) = 177.5(2)°. Key words: dinitrogen, nickel, X-ray.

Early developments in lanthanide-based dinitrogen reduction chemistry

2005 ◽  
Vol 83 (4) ◽  
pp. 375-384 ◽  
Author(s):  
William J Evans ◽  
David S Lee
Keyword(s):  
Nitrogen Fixation ◽  
Alkali Metal ◽  
Key Words ◽  
Entire Series ◽  
Dinitrogen Reduction ◽  
Dinitrogen Complex

Although the first crystallographically characterized lanthanide dinitrogen complex was reported in 1988 with samarium, it is only in recent years that this field has expanded to include fully characterized examples for the entire series of lanthanides. The development of lanthanide dinitrogen chemistry has been aided by a series of unexpected results that present some good lessons in the development of science. This review presents a chronological account of the lanthanide dinitrogen chemistry discovered in our laboratory through the summer of 2004.Key words: lanthanides, dinitrogen, reduction, alkali metal, nitrogen fixation, diazenido.

Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)2(µ-H)4 and ([NPN]Ta)2(µ-η1:η2-N2)(µ-H)2 (where NPN = PhP(CH2SiMe2NPh)2)

2005 ◽  
Vol 83 (6-7) ◽  
pp. 652-660 ◽  
Author(s):  
Michael P Shaver ◽  
Samuel A Johnson ◽  
Michael D Fryzuk
Keyword(s):  
Small Molecules ◽  
Key Words ◽  
Crystallographic Analysis ◽  
Terminal Alkynes ◽  
Dinitrogen Complex

Reaction of phenylacetylene with the dinuclear tetrahydride complex ([NPN]Ta)2(µ-H)4 gives the product ([NPN]Ta)2(µ-PhCCH)(µ-H)2 (where NPN is PhP(CH2SiMe2NPh)2). Activation of other terminal alkynes by ([NPN]Ta)2(µ-H)4 accesses ([NPN]Ta)2(µ-RCCH)(µ-H)2 (R = n-Pr, t-Bu). Crystallographic analysis of the R = Ph derivative showed it to be a bis(µ-alkylidene) bound asymmetrically to the two tantalum centres. Storage of solutions of ([NPN]Ta)2(µ-PhCCH)(µ-H)2 under vacuum promotes the loss of H2 and cleavage of the C—C bond to give a bis(µ-alkylidyne) complex, ([NPN]Ta)2(µ-CPh)(µ-CH). Addition of diphenylacetylene did not give the desired ([NPN]Ta)2(µ-CPh)2, but rather promotes a complex decomposition of the supporting [NPN] ligands. Reaction of phenylacetylene with the dinitrogen complex ([NPN]Ta)2(µ-η1:η2-N2)(µ-H)2 results in the dissociation of the bound dinitrogen and the formation of ([NPN]Ta)2(µ-PhCCH)(µ-H)2, which is identical to that derived from the reaction with the dinuclear tetrahydride. Key words: tantalum, alkyne, alkylidene, alkylidyne, amidodiphosphine, dinuclear hydride dinitrogen, activation of small molecules.

Reactivity of a low-valent chromium dinitrogen complex

2011 ◽  
Vol 369 (1) ◽  
pp. 103-119 ◽  
Author(s):  
Wesley H. Monillas ◽  
Glenn P.A. Yap ◽  
Klaus H. Theopold
Keyword(s):  
Low Valent ◽  
Dinitrogen Complex

Dinitrogen Fixation versus Metal-Metal Bond Formation in the Chemistry of Vanadium(II) Amidinates

1994 ◽  
Vol 116 (16) ◽  
pp. 7417-7418 ◽  
Author(s):  
Pietro Berno ◽  
Shoukang Hao ◽  
Ravinder Minhas ◽  
Sandro Gambarotta
Keyword(s):  
Bond Formation ◽  
Dinitrogen Fixation ◽  
Metal Bond ◽  
Metal Metal

scholarly journals Nitrogen–Carbon Bond Formation from N2 and CO2 Promoted by a Hafnocene Dinitrogen Complex Yields a Substituted Hydrazine

2007 ◽  
Vol 46 (16) ◽  
pp. 2858-2861 ◽  
Author(s):  
Wesley H. Bernskoetter ◽  
Emil Lobkovsky ◽  
Paul J. Chirik
Keyword(s):  
Bond Formation ◽  
Carbon Bond ◽  
Dinitrogen Complex

Nitrogen–Carbon Bond Formation from N2 and CO2 Promoted by a Hafnocene Dinitrogen Complex Yields a Substituted Hydrazine

2007 ◽  
Vol 119 (16) ◽  
pp. 2916-2919 ◽  
Author(s):  
Wesley H. Bernskoetter ◽  
Emil Lobkovsky ◽  
Paul J. Chirik
Keyword(s):  
Bond Formation ◽  
Carbon Bond ◽  
Dinitrogen Complex

Cover Picture: Nitrogen–Carbon Bond Formation from N2 and CO2 Promoted by a Hafnocene Dinitrogen Complex Yields a Substituted Hydrazine (Angew. Chem. Int. Ed. 16/2007)

2007 ◽  
Vol 46 (16) ◽  
pp. 2727-2727
Author(s):  
Wesley H. Bernskoetter ◽  
Emil Lobkovsky ◽  
Paul J. Chirik
Keyword(s):  
Bond Formation ◽  
Carbon Bond ◽  
Dinitrogen Complex

Carbon−Nitrogen Bond Formation via the Reaction of Terminal Alkynes with a Dinuclear Side-on Dinitrogen Complex

2004 ◽  
Vol 126 (31) ◽  
pp. 9480-9481 ◽  
Author(s):  
Lara Morello ◽  
Jason B. Love ◽  
Brian O. Patrick ◽  
Michael D. Fryzuk
Keyword(s):  
Bond Formation ◽  
Terminal Alkynes ◽  
Dinitrogen Complex ◽  
Nitrogen Bond
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