Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center

American Association for the Advancement of Science (AAAS) - Tập 301 Số 5629 - Trang 76-78 - 2003
Dmitry V. Yandulov1, Richard R. Schrock1
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 USA

Tóm tắt

Dinitrogen (N 2 ) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN 3 N] 3– triamidoamine ligands {such as [HIPTN 3 N]Mo(N 2 ), where [HIPTN 3 N] 3– is [{3,5-(2,4,6-i-Pr 3 C 6 H 2 ) 2 C 6 H 3 NCH 2 CH 2 } 3 N] 3– } in heptane. Slow addition of the proton source [{2,6-lutidinium}{BAr′ 4 }, where Ar′ is 3,5-(CF 3 ) 2 C 6 H 3 ]and reductant (decamethyl chromocene) was critical for achieving high efficiency (∼66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N 2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.

Từ khóa


Tài liệu tham khảo

10.1021/cr00106a002

10.1021/cr950055x

10.1016/S1367-5931(00)00132-0

D. C. Rees, M. K. Chan, J. Kim, Adv. Inorg. Chem.40, 89 (1996).

10.1021/cr950057h

R. R. Eady, J. Inorg. Biochem.86, 42 (2001).

10.1021/cr9500545

10.1038/360553a0

10.1021/bi00079a006

10.1073/pnas.90.3.1078

10.1002/anie.199315921

10.1126/science.1073877

A. D. Allen, C. V. Senoff, J. Chem. Soc. Chem. Commun.1965, 621 (1965).

10.1021/cr60316a001

10.1021/cr00036a008

10.1016/S0010-8545(98)00250-1

10.1016/S0010-8545(00)00264-2

10.1016/0010-8545(95)01139-G

10.1007/s007750050099

10.1016/S0010-8545(02)00183-2

10.1016/0010-8545(96)01186-1

10.1016/S0898-8838(08)60108-7

10.1021/ja00493a039

10.1016/0304-5102(87)80030-5

10.1021/ja00187a092

K. Tanaka, Y. Hozumi, T. Tanaka, Chem. Lett.1982, 1203 (1982).

10.1016/S0277-5387(00)80270-3

Pickett ( 41 ) has reported protonating a tungsten bisdinitrogen complex of this type with a stoichiometric amount of p-toluenesulfonic acid and then electrochemically reducing the hydrazido(2-) complex at –2.6 V versus ferrocene/ferricenium to yield 0.22 to 0.24 equivalents of NH 3 and 0.85 to 0.95 equivalents of reformed bisdinitrogen complex. Three sequential cycles were performed in one vessel to yield 0.73 equivalents of NH 3 .

10.1351/pac199769102197

10.1021/ic001122v

G. E. Greco, R. R. Schrock, Inorg. Chem.40, 3860 (2001).

10.1021/ja020186x

10.1021/ic020505l

D. V. Yandulov unpublished data.

10.1021/cr940053x

10.1146/annurev.physchem.49.1.337

10.1021/ja00371a017

Materials and methods are available as supporting material on Science Online.

10.1093/clinchem/8.2.130

10.1021/ac60252a045

10.1038/317652a0

Supported by NIH grant no. GM 31978 (R.R.S).

Thông tin
Thông tin xuất bản

American Association for the Advancement of Science (AAAS)

Tập 301 Số 5629

76-78

Thông tin tác giả