3-Rhoda-1,2-diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From C-N Functionalization of Ethylene. Drover, M., W.; Beh, D., W.; Kennepohl, P.; and Love, J., A. Chem. Eur. J., 20(41):13345-55, 10, 2014.
Paper
Website abstract bibtex Rh-containing metallacycles, [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NR)2 -]Cl; TPA=N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the Rh(I) ethylene complex, [(TPA)Rh(η(2) -CH2 CH2 )]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2 NNCO2 R; R=Et [3]Cl, R=iPr [4]Cl, R=tBu [5]Cl, and R=Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh(III) (Cl)(κ(1) -(C)-CH2 CH2 (NCO2 R)(NHCO2 R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NH)2 -](+) [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NAc)2 -](+) , [17]Cl. Treatment of [1]Cl with AcNNAc did not give the RhN insertion product, but instead the N,O-chelated complex [(TPA)Rh(I) (κ(2) -(O,N)-CH3 (CO)(NH)(NC(CH3 )(OCHCH2 ))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]O bond.
@article{
title = {3-Rhoda-1,2-diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From C-N Functionalization of Ethylene.},
type = {article},
year = {2014},
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keywords = {Electronic Structure,Organometallic Chemistry},
pages = {13345-55},
volume = {20},
websites = {http://www.ncbi.nlm.nih.gov/pubmed/25169120},
month = {10},
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abstract = {Rh-containing metallacycles, [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NR)2 -]Cl; TPA=N,N,N,N-tris(2-pyridylmethyl)amine have been accessed through treatment of the Rh(I) ethylene complex, [(TPA)Rh(η(2) -CH2 CH2 )]Cl ([1]Cl) with substituted diazenes. We show this methodology to be tolerant of electron-deficient azo compounds including azo diesters (RCO2 NNCO2 R; R=Et [3]Cl, R=iPr [4]Cl, R=tBu [5]Cl, and R=Bn [6]Cl) and a cyclic azo diamide: 4-phenyl-1,2,4-triazole-3,5-dione (PTAD), [7]Cl. The latter complex features two ortho-fused ring systems and constitutes the first 3-rhoda-1,2-diazabicyclo[3.3.0]octane. Preliminary evidence suggests that these complexes result from N-N coordination followed by insertion of ethylene into a [Rh]N bond. In terms of reactivity, [3]Cl and [4]Cl successfully undergo ring-opening using p-toluenesulfonic acid, affording the Rh chlorides, [(TPA)Rh(III) (Cl)(κ(1) -(C)-CH2 CH2 (NCO2 R)(NHCO2 R)]OTs; [13]OTs and [14]OTs. Deprotection of [5]Cl using trifluoroacetic acid was also found to give an ethyl substituted, end-on coordinated diazene [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NH)2 -](+) [16]Cl, a hitherto unreported motif. Treatment of [16]Cl with acetyl chloride resulted in the bisacetylated adduct [(TPA)Rh(III) (κ(2) -(C,N)-CH2 CH2 (NAc)2 -](+) , [17]Cl. Treatment of [1]Cl with AcNNAc did not give the RhN insertion product, but instead the N,O-chelated complex [(TPA)Rh(I) (κ(2) -(O,N)-CH3 (CO)(NH)(NC(CH3 )(OCHCH2 ))]Cl [23]Cl, presumably through insertion of ethylene into a [Rh]O bond.},
bibtype = {article},
author = {Drover, Marcus W and Beh, Daniel W and Kennepohl, Pierre and Love, Jennifer A},
journal = {Chem. Eur. J.},
number = {41}
}