skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Princeton University, Frick Laboratory 292 Princeton 08544 USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1418864
Grant/Contract Number:
SC0006498
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 8; Related Information: CHORUS Timestamp: 2018-02-13 05:28:27; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Bezdek, Máté J., and Chirik, Paul J. Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer. Germany: N. p., 2018. Web. doi:10.1002/anie.201708406.
Bezdek, Máté J., & Chirik, Paul J. Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer. Germany. doi:10.1002/anie.201708406.
Bezdek, Máté J., and Chirik, Paul J. 2018. "Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer". Germany. doi:10.1002/anie.201708406.
@article{osti_1418864,
title = {Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer},
author = {Bezdek, Máté J. and Chirik, Paul J.},
abstractNote = {},
doi = {10.1002/anie.201708406},
journal = {Angewandte Chemie (International Edition)},
number = 8,
volume = 57,
place = {Germany},
year = 2018,
month = 1
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on January 31, 2019
Publisher's Accepted Manuscript

Save / Share:
  • Treating Rh{sub 2}(CO){sub 2}Cl{sub 2}({mu}-dxpm){sub 2} (dxpm = bis(diphenylphosphino)methane (dppm) or bis(dimethylphosphino)methane (dmpm)) with 2 equiv of LiNHR (R = Me, Ph, p-MeOPh, p-MePh, o-MePh, o,o{prime}-Me{sub 2}Ph, p-FPh, p-BrPh, p-NO{sub 2}Ph) gives Rh{sub 2}({mu}-NR)(CO){sub 2}({mu}-dxpm){sub 2} (1), its tautomer Rh{sub 2}({mu}-NHR)(CO){sub 2}({mu}-dxpm)({mu}-dxpm-H) (2), or equilibrium mixtures of 1 and 2 (1/2) (dxpm-H = bis(diphenylphosphino)methanide or bis(dimethylphosphino)methanide). Both tautomers have been characterized by x-ray crystal structure determinations. Crystals of tautomer 1 (dppm, R = p-NO{sub 2}Ph) from CH{sub 2}Cl{sub 2}/Et{sub 2}O are monoclinic (C2/c) with a = 11.337 (4) {angstrom}, b = 36.451 (8) {angstrom}, c = 12.821 (3) {angstrom}, {beta}more » = 90.59 (3){degree}, V = 5297.7 {angstrom}{sup 3}, and Z = 4. The structure of 2 (dppm, R = Me) clearly shows the presence of the dppm-H and the NHMe ligands. Crystals from toluene are triclinic (P{anti 1}) with a = 10.459 (12) {angstrom}, b = 14.348 (3) {angstrom}, c = 20.867 (6) {angstrom}, {alpha} = 104.96 (2){degree}, {beta} = 101.12 (4){degree}, {gamma} = 93.47 (6){degree}, V = 2,948.3 {angstrom}{sup 3}, and Z = 2.« less
  • Interest in late transition metal chemistry is focused on the second- and third-row metals Rh, Ir, Pd, Pt, Ag, and Au and primarily involves oxo (O{sup 2{minus}}) complexes. However, the major synthetic route to these complexes involves deprotonation of the corresponding hydroxo (OH{sup {minus}}) and amido (RNH{sup {minus}}) complexes. Thus, the authors are interested in the acid/base chemistry of these conjugate acid/base pairs. In addition, as has been pointed out by Driver and Hartwig, the acid/base properties of the synthetically important alkali metal analogues is fundamental to their chemistry and should be expected to be similarly important for the transitionmore » metal complexes. Here the authors report a series of Pt(II) primary aryl amido complexes prepared by aminolysis of the corresponding hydroxo complexes. Deprotonation of these complexes was explored with the goal of increasing the understanding of ancillary ligand effects on the acid/base chemistry of these Pt(II) complexes. The authors have also isolated mixed amido-hydroxo complexes and unique dihydrazido complexes and explored their deprotonation chemistry.« less
  • Treating tautomeric mixtures of Rh[sub 2]([mu]-NR)(CO)[sub 2]([mu]-dppm)[sub 2] and Rh[sub 2]([mu]-NHR)(CO)[sub 2]([mu]-dppm-H)([mu]-dppm) (dppm = bis(diphenylphosphino)methane, dppm-H = bis(diphenylphosphino)methanide) (1/2) or Rh[sub 2]([mu]-NHMe)(CO)[sub 2]([mu]-dppm-H)([mu]-dppm) (2; R = Me) in CH[sub 2]Cl[sub 2] or benzene with 1 equiv of CO gives Rh[sub 2]([mu]-[eta][sup 1]:[eta][sup 1]-RNCO)(CO)[sub 2]([mu]-dppm)[sub 2] (3; R = Me, Ph, [rho]-MePh, [rho]-FPh, [rho]-BrPh). Excess CO gives Rh[sub 2]([mu]-CO)(CO)[sub 2]([mu]-dppm)[sub 2], RNCO, and (RNH)[sub 2]CO (R = Ph, [rho]-MePh, [rho]-MeOPh, [rho]-BrPh, p[rho]-[rho]FPh, [omicron]-MePh) or Rh[sub 2][[mu]-[eta][sup 1]:[eta][sup 1]-C(O)N(Me)C(O)]([mu]-CO)(CO)[sub 2]([mu]-dppm)[sub 2] (4) and Rh[sub 2]([mu]-CO)(CO)[sub 2]([mu]-dppm)[sub 2] (R = Me). An x-ray crystal structure determination of 4 shows a cradle geometry withmore » bridging cis phosphines and a dimetallacycloimide structure formed by insertion of CO into both Rh-N bonds. Treating Rh[sub 2]([mu]-[eta][sup 1]:[eta][sup 1]-RNCO)(CO)[sub 2]([mu]-dppm)[sub 2] (3; R = [rho]-FPh) with [rho]-MePhNCO under a CO atmosphere gives a mixture of ureas, [([rho]-MePh)NH][sub 2]CO, ([rho]-MePh)NHCOHN([rho]-FPh), and [([rho]-FPh)NH][sub 2]CO.« less