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Title: Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.

Abstract

Complexes [{l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}({mu}-H)]{sup +}BF{sub 4}{sup -} (M = Fe, Ru, Os; 1a-cH{sup +}BF{sub 4}{sup -}), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH{sub 2}, Me{sub 2}NH, Et{sub 3}N, morpholine) to give the deprotonated complexes {l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the {nu}(CO) values. Molecular structures of 1a-cH{sup +}BF{sub 4}{sup -}, as determined by X-ray diffraction studies, and [{l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}({mu}-H)]{sup +}OTf{sup -} (1bD{sup +}TfO{sup -}), as determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.

Authors:
; ; ; ;
Research Org.:
Intense Pulsed Neutron Source (IPNS), Argonne National Laboratory (ANL), Argonne, IL (US); Iowa State Univ.
Sponsoring Org.:
USDOE
OSTI Identifier:
15004078
DOE Contract Number:  
W-31-109-ENG-38
Resource Type:
Journal Article
Journal Name:
Organometallics ; 21: 3292-3296
Additional Journal Information:
Journal Volume: 21; Journal Issue: 15; Related Information: 2002; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; CHEMICAL REACTION KINETICS; ORGANOMETALLIC COMPOUNDS; IRON COMPLEXES; RUTHENIUM COMPLEXES; OSMIUM COMPLEXES; MOLECULAR STRUCTURE; SYNTHESIS; CARBONYLS; NEUTRON DIFFRACTION; X-RAY DIFFRACTION; intense pulsed neutron source

Citation Formats

Ovchinnikov, M. V., Wang, X., Schultz, A. J., Angelici, R. J., and IPNS. Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.. United States: N. p., Web.
Ovchinnikov, M. V., Wang, X., Schultz, A. J., Angelici, R. J., & IPNS. Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.. United States.
Ovchinnikov, M. V., Wang, X., Schultz, A. J., Angelici, R. J., and IPNS. . "Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.". United States.
@article{osti_15004078,
title = {Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.},
author = {Ovchinnikov, M. V. and Wang, X. and Schultz, A. J. and Angelici, R. J. and IPNS},
abstractNote = {Complexes [{l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}({mu}-H)]{sup +}BF{sub 4}{sup -} (M = Fe, Ru, Os; 1a-cH{sup +}BF{sub 4}{sup -}), which feature a protonated metal-metal bond, were synthesized. While the Fe and Os complexes react with nucleophilic amines (ammonia, MeNH{sub 2}, Me{sub 2}NH, Et{sub 3}N, morpholine) to give the deprotonated complexes {l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}, the Ru complex reacts with amines by undergoing attack at a CO ligand. These differences in reactivity can be understood by considering the CO ligands in the Ru complex to be more electrophilic than those in the analogous Fe and Os complexes, as indicated by the {nu}(CO) values. Molecular structures of 1a-cH{sup +}BF{sub 4}{sup -}, as determined by X-ray diffraction studies, and [{l_brace}({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}{r_brace}M{sub 2}(CO){sub 4}({mu}-H)]{sup +}OTf{sup -} (1bD{sup +}TfO{sup -}), as determined by a neutron diffraction study, show that the bridging hydride ligand is sterically concealed and therefore slow to undergo deprotonation upon reaction with bases.},
doi = {},
journal = {Organometallics ; 21: 3292-3296},
issn = {0276-7333},
number = 15,
volume = 21,
place = {United States},
year = {},
month = {}
}