Journal of the American Chemical Society
Communication
Functionalization by Uranium Multimetallic Complexes. Nat. Chem.
2019, 11, 154−160.
M. E.; Ziller, J. W.; Evans, W. J. (C5Me4H)1−-Based Reduction of
Dinitrogen by the Mixed Ligand Tris(polyalkylcyclopentadienyl)
Lutetium and Yttrium Complexes, (C5Me5)3−x(C5Me4H)xLn. Chem.
Sci. 2011, 2, 1992−1996. (h) Fieser, M. E.; Bates, J. E.; Ziller, J. W.;
Furche, F.; Evans, W. J. Dinitrogen Reduction via Photochemical
Activation of Heteroleptic Tris(cyclopentadienyl) Rare-Earth Com-
plexes. J. Am. Chem. Soc. 2013, 135, 3804−3807.
(6) Ragnarsson, U. Synthetic Methodology for Alkyl Substituted
Hydrazines. Chem. Soc. Rev. 2001, 30, 205−220.
(7) (a) Pickett, C. J.; Leigh, G. J. Towards a Nitrogen-Fixing Cycle:
Electrochemical Reduction of a Hydrazido-Complex of Molybdenum-
(IV) under N2 to Yield the Dialkylhydrazine and a Molybdenum(0)
Dinitrogen Complex. J. Chem. Soc., Chem. Commun. 1981, 1033−
1035. (b) Hidai, M.; Mizobe, Y. Recent Advances in the Chemistry of
Dinitrogen Complexes. Chem. Rev. 1995, 95, 1115−1133. (c) Hidai,
M. Chemical Nitrogen Fixation by Molybdenum and Tungsten
Complexes. Coord. Chem. Rev. 1999, 185−186, 99−108. (d) Bern-
skoetter, W. H.; Lobkovsky, E.; Chirik, P. J. Nitrogen−Carbon Bond
Formation from N2 and CO2 Promoted by a Hafnocene Dinitrogen
Complex Yields a Substituted Hydrazine. Angew. Chem., Int. Ed. 2007,
46, 2858−2861. (e) Knobloch, D. J.; Toomey, H. E.; Chirik, P. J.
Carboxylation of an ansa-Zirconocene Dinitrogen Complex: Regio-
specific Hydrazine Synthesis from N2 and CO2. J. Am. Chem. Soc.
2008, 130, 4248−4249. (f) Knobloch, D. J.; Benito-Garagorri, D.;
Bernskoetter, W. H.; Keresztes, I.; Lobkovsky, E.; Toomey, H.;
Chirik, P. J. Addition of Methyl Triflate to a Hafnocene Dinitrogen
Complex: Stepwise N2 Methylation and Conversion to a Hafnocene
Hydrazonato Compound. J. Am. Chem. Soc. 2009, 131, 14903−14912.
(g) Nakanishi, Y.; Ishida, Y.; Kawaguchi, H. Nitrogen-Carbon Bond
Formation by Reactions of a Titanium-Potassium Dinitrogen
Complex with Carbon Dioxide, tert-Butyl Isocyanate, and Phenyl-
allene. Angew. Chem., Int. Ed. 2017, 56, 9193−9197.
(8) (a) Fryzuk, M. D.; Johnson, S. A.; Patrick, B. O.; Albinati, A.;
Mason, S. A.; Koetzle, T. F. New Mode of Coordination for the
Dinitrogen Ligand: Formation, Bonding, and Reactivity of a Tantalum
Complex with a Bridging N2 Unit That Is Both Side-On and End-On.
J. Am. Chem. Soc. 2001, 123, 3960−3973. (b) Morello, L.; Love, J. B.;
Patrick, B. O.; Fryzuk, M. D. Carbon−Nitrogen Bond Formation via
the Reaction of Terminal Alkynes with a Dinuclear Side-on
Dinitrogen Complex. J. Am. Chem. Soc. 2004, 126, 9480−9481.
(c) Bernskoetter, W. H.; Olmos, A. V.; Pool, J. A.; Lobkovsky, E.;
Chirik, P. J. N−C Bond Formation Promoted by a Hafnocene
Dinitrogen Complex: Comparison of Zirconium and Hafnium
Congeners. J. Am. Chem. Soc. 2006, 128, 10696−10697. (d) Hirotsu,
M.; Fontaine, P. P.; Zavalij, P. Y.; Sita, L. R. Extreme N≡N Bond
Elongation and Facile N-Atom Functionalization Reactions within
two Structurally Versatile New Families of Group 4 Bimetallic “Side-
on-Bridged” Dinitrogen Complexes for Zirconium and Hafnium. J.
Am. Chem. Soc. 2007, 129, 12690−12692. (e) Ballmann, J.; Yeo, A.;
Patrick, B. O.; Fryzuk, M. D. Carbon−Nitrogen Bond Formation by
the Reaction of 1,2-Cumulenes with a Ditantalum Complex
Containing Side-on- and End-on-Bound Dinitrogen. Angew. Chem.,
Int. Ed. 2011, 50, 507−510.
(10) For selected reports on (N2)3− and other rare-earth metal
́
dinitrogen complexes, see: (a) Dube, T.; Conoci, S.; Gambarotta, S.;
Yap, G. P. A.; Vasapollo, G. Tetrametallic Reduction of Dinitrogen:
Formation of a Tetranuclear Samarium Dinitrogen Complex. Angew.
Chem., Int. Ed. 1999, 38, 3657−3659. (b) Evans, W. J.; Fang, M.;
Zucchi, G.; Furche, F.; Ziller, J. W.; Hoekstra, R. M.; Zink, J. I.
Isolation of Dysprosium and Yttrium Complexes of a Three-Electron
Reduction Product in the Activation of Dinitrogen, the (N2)3− Rdical.
J. Am. Chem. Soc. 2009, 131, 11195−11202. (c) Evans, W. J.; Fang,
M.; Bates, J. E.; Furche, F.; Ziller, J. W.; Kiesz, M. D.; Zink, J. I.
Isolation of a Radical Dianion of Nitrogen Oxide (NO)2−. Nat. Chem.
2010, 2, 644−647. (d) Fang, M.; Bates, J. E.; Lorenz, S. E.; Lee, D. S.;
Rego, D. B.; Ziller, J. W.; Furche, F.; Evans, W. J. (N2)3− Radical
Chemistry via Trivalent Lanthanide Salt/Alkali Metal Reduction of
Dinitrogen: New Syntheses and Examples of (N2)2− and (N2)3−
Complexes and Density Functional Theory Comparisons of Closed
Shell Sc3+, Y3+, Lu3+ versus 4f9 Dy3+. Inorg. Chem. 2011, 50, 1459−
1469. (e) Fang, M.; Lee, D. S.; Ziller, J. W.; Doedens, R. J.; Bates, J.
E.; Furche, F.; Evans, W. J. Synthesis of the (N2)3− Radical from Y2+
and Its Protonolysis Reactivity to Form (N2H2)2− via the Y[N-
(SiMe3)2]3/KC8 Reduction System. J. Am. Chem. Soc. 2011, 133,
3784−3787. (f) Rinehart, J. D.; Fang, M.; Evans, W. J.; Long, J. R.
Strong Exchange and Magnetic Blocking in N23−-Radical-Bridged
Lanthanide Complexes. Nat. Chem. 2011, 3, 538−542. (g) Meihaus,
M. R.; Corbey, J. F.; Fang, M.; Ziller, J. W.; Long, J. R.; Evans, W. J.
Influence of an Inner-Sphere K+ Ion on the Magnetic Behavior of
3−
N2 Radical-Bridged Dilanthanide Complexes Isolated Using an
External Magnetic Field. Inorg. Chem. 2014, 53, 3099−3107.
(h) Demir, S.; Gonzalez, M. I.; Darago, L. E.; Evans, W. J.; Long, J.
R. Giant Coercivity and High Magnetic Blocking Temperatures for
3−
N2 Radical-Bridged Dilanthanide Complexes upon Ligand Dis-
sociation. Nat. Commun. 2017, 8, 2144.
(11) Walter, M. D. Recent Advances in Transition Metal-Catalyzed
Dinitrogen Activation. Adv. Organomet. Chem. 2016, 65, 261−377.
(12) Tanabe, Y. Group 3 Transition Metal, Lanthanide, and
Actinide−Dinitrogen Complexes. In Transition Metal−Dinitrogen
Complexes; Nishibayashi, Y., Ed.; Wiley-VCH: Weinheim, Germany,
2019; Chapter 9, pp 441−474.
(13) Fieser, M. E.; Woen, D. H.; Corbey, J. F.; Mueller, T. J.; Ziller,
J. W.; Evans, W. J. Raman Spectroscopy of the N−N Bond in Rare
Earth Dinitrogen Complexes. Dalton Trans. 2016, 45, 14634−14644.
(14) Woen, D. H.; Chen, G. P.; Ziller, J. W.; Boyle, T. J.; Furche, F.;
Evans, W. J. End-on Bridging Dinitrogen Complex of Scandium. J.
Am. Chem. Soc. 2017, 139, 14861−14864.
(15) (a) Pool, J. A.; Lobkovsky, E.; Chirik, P. J. Hydrogenation and
Cleavage of Dinitrogen to Ammonia with a Zirconium Complex.
Nature 2004, 427, 527−530. (b) Bernskoetter, W. H.; Olmos, A. V.;
Lobkovsky, E.; Chirik, P. J. N2 Hydrogenation Promoted by a Side-on
Bound Hafnocene Dinitrogen Complex. Organometallics 2006, 25,
(9) For selected reports on (N2)2−−rare-earth metal complexes, see:
(a) Evans, W. J.; Ulibarri, T. A.; Ziller, J. W. Isolation and X-ray
Crystal Structure of the First Dinitrogen Complex of an f-Element
Metal, [(C5Me5)2Sm]2N2. J. Am. Chem. Soc. 1988, 110, 6877−6879.
(b) Evans, W. J.; Lee, D. S. Early Developments in Lanthanide-Based
Dinitrogen Reduction Chemistry. Can. J. Chem. 2005, 83, 375−384.
(c) Evans, W. J.; Lee, D. S.; Ziller, J. W.; Kaltsoyannis, N. Trivalent
[(C5Me5)2(THF)Ln]2(μ-η2:η2-N2) Complexes as Reducing Agents
Including the Reductive Homologation of CO to a Ketene
Carboxylate, (μ-η4-O2C−CCO)2−. J. Am. Chem. Soc. 2006,
128, 14176−14184. (d) Cheng, J.; Takats, J.; Ferguson, M. J.;
McDonald, R. Heteroleptic Tm(II) Complexes: One more Success
for Trofimenko’s Scorpionates. J. Am. Chem. Soc. 2008, 130, 1544−
1545. (e) Jaroschik, F.; Momin, A.; Nief, F.; Le Goff, X.-F.; Deacon,
G. B.; Junk, P. C. Dinitrogen Reduction and C−H Activation by the
Divalent Organoneodymium Complex [(C5H2tBu3)2Nd(μ-I)K([18]-
crown-6)]. Angew. Chem., Int. Ed. 2009, 48, 1117−1121. (f) Demir,
S.; Lorenz, S. E.; Fang, M.; Furche, F.; Meyer, G.; Ziller, J. W.; Evans,
W. J. Synthesis, Structure, and Density Functional Theory Analysis of
a Scandium Dinitrogen Complex, [(C5Me4H)2Sc]2(μ-η2:η2-N2). J.
Am. Chem. Soc. 2010, 132, 11151−11158. (g) Mueller, T. J.; Fieser,
1021−1027. (c) Morello, L.; Joao Ferreira, M.; Patrick, B. O.; Fryzuk,
̃
M. D. Side-on Bound Dinitrogen Complex of Zirconium Supported
by a P2N2 Macrocyclic Ligand. Inorg. Chem. 2008, 47, 1319−1323.
(16) Fagan, P. J.; Manriquez, J. M.; Vollmer, S. H.; Day, C. S.; Day,
V. W.; Marks, T. J. Insertion of Carbon Monoxide into Metal-
Nitrogen Bonds. Synthesis, Chemistry, Structures, and Structural
Dynamics of Bis(pentamethylcyclopentadienyl) Organoactinide Dia-
lkylamides and η2-Carbamoyls. J. Am. Chem. Soc. 1981, 103, 2206−
2020.
(17) Wang, B.; Kang, X.; Nishiura, M.; Luo, Y.; Hou, Z. Isolation,
Structure and Reactivity of a Scandium Boryl Oxycarbene Complex.
Chem. Sci. 2016, 7, 803−809.
E
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX