Inorganic Chemistry
Article
(2) (a) Evans, W. J.; Davis, B. L. Chem. Rev. 2002, 102, 2119.
(b) Evans, W. J. J. Organomet. Chem. 2002, 647, 2. (c) Evans, W. J.
Coord. Chem. Rev. 2000, 206−207, 263. (d) Hou, Z.-M; Yoda, C.;
Koizumi, T.-a.; Nishiura, M.; Wakatsuki, Y.; Fukuzawa, S.-i.; Takats, J.
Organometallics 2003, 22, 3586. (e) Arndt, S.; Okuda, J. Chem. Rev.
2002, 102, 1953. (f) Hou, Z.-M; Wakatsuki, Y. J. Organomet. Chem.
2002, 647, 61. (g) Kirillov, E.; Saillard, J.-Y.; Carpentier, J.-F. Coord.
Chem. Rev. 2005, 249, 1221. (h) Bochkarev, M. N. Coord. Chem. Rev.
2004, 248, 835.
(3) (a) Hou, Z.-M.; Koizumi, T.-a.; Nishiura, M.; Wakatsuki, Y.
Organometallics 2001, 20, 3323. (b) Deng, M. Y.; Yao, Y. M.; Shen, Q.;
Zhang, Y.; Sun, J. Dalton Trans. 2004, 944. (c) Deacon, G. B.;
Fanwick, P. E.; Gitlits, A.; Rothwell, I. P.; Skelton, B. W.; White, A. H.
Eur. J. Inorg. Chem. 2001, 1505. (d) Zhou, H.; Guo, H. D.; Yao, Y. M.;
Zhou, L. Y.; Sun, H. M.; Sheng, H. T.; Zhang, Y.; Shen, Q. Inorg.
Chem. 2007, 46, 958. (e) Hou, Z.-M; Zhang, Y.; Nishiura, M.;
Wakatsuki, Y. Organometallics 2003, 22, 129. (f) Panda, T. K.; Zulys,
A.; Gamer, M. T.; Roesky, P. W. J. Organomet. Chem. 2005, 690, 5078.
(g) Guo, H. D.; Zhou, H.; Yao, Y. M.; Zhang, Y.; Shen, Q. Dalton
Trans. 2007, 3555. (h) Dugah, D. T.; Skelton, B. W.; Delbridge, E. E.
Dalton Trans. 2009, 1436. (i) Zhou, L.; Wang, J.; Zhang, Y.; Yao, Y.;
Shen, Q. Inorg. Chem. 2007, 46, 5763. (j) Edelmann, F. T.; Freckmann,
D. M. M.; Schumann, H. Chem. Rev. 2002, 102, 1851. (k) Cui, P.;
Chen, Y.; Li, G.; Xia, W. Angew. Chem., Int. Ed. 2008, 47, 9944.
(l) Cole, M. L.; Junk, P. C. Chem. Commun. 2005, 2695.
(m) Heitmann, D.; Jones, C.; Junk, P. C.; Lippert, K.-A.; Stasch, A.
Dalton Trans. 2007, 187.
in agreement with the ionic radii difference between Yb(II) and
Yb(III) (0.155 Å),21b indicative of oxidation of Yb(II) in
complex 3.
The two almost equal Yb−N bond lengths (in error limits,
2.365(3) and 2.379(3) Å in complex 6; and 2.328(10) and
2.313(10) Å in complex 7) and a delocalized NCCNπ system
(NC bonds, 1.329(5) and 1.335(4) Å in complex 6 and
1.385(17) and 1.348(15) Å in complex 7; C−C bond, 1.396(5)
Å in complex 6 and 1.395(18) Å in complex 7) were observed
in the YbDAD part of both complexes. The coordination
pattern of the DAD ligand to a Yb ion here is usual in the
systems with Cp complexes.21a−d
The geometry parameters of complexes 6 and 7 indicate
unequivocally reduced radical-anionic character of the
diazabutadiene ligands and the 3+ oxidation state of Yb metal
in both complexes.
The well-known bond valence sum (BVS) could be used as a
convenient method to estimate the oxidation state of a central
metal in a complex.23 To further confirm the central metal Yb
in complexes 6 and 7 being in the +3 oxidation state, the BVS
calculation for both complexes was made. Indeed, the values are
equal to 3.37 for complex 6 and 3.39 for complex 7.
CONCLUSION
■
In summary, four kinds of Ln(II) complexes supported by
bridged bis(amidinates) ligand L, [{YbI(DME)2}2(μ2-L)] (1),
[{Li(DME)3}+]2[{(EuI)2(μ2-I)2(μ3-L)2(Li)4}(μ6-O)]2‑ (2),
[Yb3(μ2-L)3] (3) and [Eu(μ2-L)(THF)]2 (4), were synthesized
and structurally characterized. Complex 3 can serve as a one-
electron reducing agent to reduce CyNCNCy and
(4) Bambirra, S.; Meetsma, A.; Hessen, B.; Teuben, J. H.
Organometallics 2001, 20, 782.
(5) (a) Wang, J.; Cai, T.; Yao, Y.; Zhang, Y.; Shen, Q. Dalton Trans.
2007, 5275. (b) Wang, J.; Yao, Y.; Zhang, Y.; Shen, Q. Inorg. Chem.
2009, 48, 744. (c) Wang, J.; Sun, H.; Yao, Y.; Zhang, Y.; Shen, Q.
Polyhedron 2008, 27, 1977.
(6) (a) Wang, J.; Xu, F.; Cai, T.; Shen, Q. Org. Lett. 2008, 10, 445.
(b) Wang, J.; Li, J.; Xu, F.; Shen, Q. Adv. Synth. Catal. 2009, 351, 1363.
(7) Pan, C. L.; Chen, W.; Song, S.; Zhang, H.; Li, X. Inorg. Chem.
2009, 48, 6344.
diazabutadienes, [2,6-iPr2C6H3NCRCRNC6H3 Pr2-2,6]
i
(R = H, Me), respectively, with the formation of Yb(III)
complex bearing an oxalamidinate ligand [LYb{(NCy)2CC-
(NCy)2}YbL] (5) and the Yb(III) complexes with a
d i a z a b u t a d i e n e r a d i c a l a n i o n [ L Y b -
(8) Wang, J.; Yao, Y.; Cheng, J.; Pang, X. A.; Zhang, Y.; Shen, Q. J.
Mol. Struct. 2005, 743, 229.
(iPr2C6H3NCRCRNC6H3 Pr2)] (R = H (6), CH3 (7)).
i
(9) Turkmen, H.; Çetinkaya, B. J. Organomet. Chem. 2006, 691, 3749.
̈
(10) Wedler, M.; Noltemeyer, M.; Pieper, U.; Schmidt, H.-G.; Stalke,
D.; Edelmann, F. T. Angew. Chem., Int. Ed. Engl. 1990, 102, 941.
(11) (a) Heckmann, G.; Niemeyer, M. J. Am. Chem. Soc. 2000, 122,
4227. (b) Hasinoff, L.; Takats, J.; Zhang, X. W. J. Am. Chem. Soc. 1994,
116, 8833.
ASSOCIATED CONTENT
■
S
* Supporting Information
X-ray crystallographic data of complexes 1−7 are available free
(12) (a) Evans, W. J.; Hozbor, M. A. J. Organomet. Chem. 1987, 326,
299. (b) Tilley, T. D.; Andersen, R. A.; Spencer, B.; Ruben, H.; Zalkin,
A.; Templeton, D. H. Inorg. Chem. 1980, 19, 2999.
(13) Yao, S.; Chan, H.-S.; Lam, C.-K.; Lee, H. K. Inorg. Chem. 2009,
48, 9936.
(14) Shannon, R. D. Acta Crystallogr. 1976, 32, 751.
(15) (a) Hill, M. S.; Hitchcock, P. B.; Mansell, S. M. Dalton Trans.
2006, 1544. (b) Whitener, G. D.; Hagadorn, J. R.; Arnold, J. J. Chem.
Soc., Dalton Trans. 1999, 1249. (c) Bai, S. D.; Guo, J. P.; Liu, D. S.
Dalton Trans. 2006, 2244.
AUTHOR INFORMATION
Corresponding Author
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
China (Grants 21132002 and 20972107), a project funded by
the Priority Academic Program Development of Jiangsu Higher
Education Institutions for financial support.
(16) Giesbrecht, G. R.; Shafir, A.; Arnold, J. J. Chem. Soc., Dalton
Trans. 1999, 3601.
(17) Evans, W. J.; Hughes, L. A.; Hanusa, T. P. Organometallics 1986,
5, 1285.
(18) (a) Cole, M. L.; Deacon, G. B.; Forsyth, C. M.; Junk, P. C.;
Ceron, D. P.; Wang, J. Dalton Trans. 2010, 6732. (b) Du, Z.; Zhang,
́
REFERENCES
■
Y.; Yao, Y.; Shen, Q. Dalton Trans. 2011, 7639. (c) Deacon, G. B.;
Forsyth, C. M.; Junk, P. C.; Wang, J. Inorg. Chem. 2007, 46, 10022.
(d) Deng, M. Y.; Yao, Y. M.; Zhang, Y.; Shen, Q. Chem. Commun.
2004, 2742.
(19) Du, Z.; Zhou, H.; Yao, H.; Zhang, Y.; Yao, Y.; Shen, Q. Chem.
Commun. 2011, 3595.
(1) (a) Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem. Soc. 1980,
102, 2693. (b) Kagan, H. B. In Fundamental and Technological Aspects
̀
of Organo-f-Element Chemistry; Marks, T. J., Fragala, I. L., Eds.; Reidel:
Dordrecht, The Netherlands, 1985; p 49. (c) Collin, J.; Giuseppone,
N.; Van de Weghe, P. Coord. Chem. Rev. 1998, 117, 178. (d) Hou, Z.-
M.; Wakatsuki, Y. Coord. Chem. Rev. 2002, 231, 1. (e) Edmonds, D. J.;
Johnston, D.; Procter, D. J. Chem. Rev. 2004, 104, 3371. (f) Gromada,
J.; Carpentier, J.-F.; Mortreux, A. Coord. Chem. Rev. 2004, 248, 397.
(20) (a) Tom Dieck, H.; Renk, I. W. Chem. Ber. 1971, 104, 110.
(b) Tom Dieck, H.; Franz, K.-D.; Hoffmann, F. Chem. Ber. 1975, 108,
4159
dx.doi.org/10.1021/ic202505d | Inorg. Chem. 2012, 51, 4151−4160