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• W2742895299 abstract "Abstract The reactions of CuX 2 · n H 2 O (X = ClO 4 , BF 4 ), Cu turnings and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) with excess 1,5-cyclooctadiene (cod) in Me 2 CO under C 2 H 4 afforded dinuclear Cu(I)-bptz/η 2 ,η 2 -cod-X complexes {( 1 ) and ( 4 )} and dinuclear Cu(I)-2,5-H 2 bptz/η 2 ,η 2 -cod-X complexes {( 2 ) and ( 5 )}. In complexes 1 and 4 , each Cu(I) atom is coordinated by two chelate N atoms of bptz and two C C bonds of η 2 ,η 2 -cod in the distorted tetrahedral geometry to produce a transoid dinuclear structure. It should be noted that the redox state of the central tetrazine ring is electrochemically neutral. In complexes 2 and 5 , each Cu(I) atom is coordinated by two chelate N atoms of 2,5-H 2 bptz and two C C bonds of η 2 ,η 2 -cod in the distorted tetrahedral geometry to afford a transoid dinuclear structure in the 2,5-dihydro form. In contrast, the reactions of Cu(BF 4 ) 2 · n H 2 O, Cu turnings and bptz with excess 2,5-norbornadiene (nbd) in MeEtCO under C 2 H 4 afforded Cu(I)-2,5-H 2 bptz/η 2 -nbd-BF 4 complex ( 6 ). Each Cu(I) atom is coordinated by two chelate N atoms in bptz and one C C bond in η 2 -nbd to form a transoid dinuclear structure in the 2,5-dihydro form. These facts show that the flexible cod can preferentially produce a Cu(I)-cyclodiene complex in the η 2 ,η 2 -mode (complexes 1 , 2 , 4 and 5 ) while the rigid nbd can produce a Cu(I)-cyclodiene complex in the η 2 -mode (complex 6 ). Furthermore, the reaction of Cu(NO 3 ) 2 ·3H 2 O, Cu turnings and bptz with excess nbd in Me 2 CO under C 2 H 4 afforded tetranuclear Cu(I)-4,5-H 2 bptz-NO 3 complex ( 7 ) containing a unique anionic [Cu 2 (nbd)(NO 3 ) 4 ] 2− moiety. In the cationic [Cu 4 (4,5-H 2 bptz) 4 ] 4+ moiety, four Cu(I) atoms are bridged by four 4,5-H 2 bptz ligands to form a [4 × 4] grid-like tetranuclear structure with two 4,5-H 2 bptz ligands lying above the Cu 4 mean plane and two lying below. In the anionic [Cu 2 (nbd)(NO 3 ) 4 ] 2− moiety, the two Cu atoms are bridged by one nbd ligand in the μ 2 -η 2 ,η 2 -mode." @default.
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• W2742895299 date "2017-10-01" @default.
• W2742895299 modified "2023-10-18" @default.
• W2742895299 title "Structural diversity of copper(I) cyclodiene complexes bridged by 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine" @default.
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• W2742895299 doi "https://doi.org/10.1016/j.ica.2017.08.002" @default.
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