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@article{
 title = {3-Rhoda-1,2-diazacyclopentanes: A Series of Novel Metallacycle Complexes Derived From C-N Functionalization of Ethylene.},
 type = {article},
 year = {2014},
 identifiers = {[object Object]},
 keywords = {Electronic Structure,Organometallic Chemistry},
 pages = {13345-55},
 volume = {20},
 websites = {http://www.ncbi.nlm.nih.gov/pubmed/25169120},
 month = {10},
 day = {6},
 id = {5cb2abec-d96a-3949-825c-09bbe0de796d},
 created = {2017-09-06T15:15:01.406Z},
 accessed = {2014-10-19},
 file_attached = {true},
 profile_id = {8c5f55f8-b69e-30e2-981b-01f0d567bbfe},
 last_modified = {2017-09-06T15:25:32.852Z},
 read = {true},
 starred = {false},
 authored = {true},
 confirmed = {true},
 hidden = {false},
 private_publication = {false},
 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 NNCO2 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 AcNNAc did not give the RhN insertion product, but instead the N,O-chelated complex [(TPA)Rh(I) (κ(2) -(O,N)-CH3 (CO)(NH)(NC(CH3 )(OCHCH2 ))]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}
}