Structural diversity of copper(I) cyclodiene complexes bridged by 3,6-bis (2-pyridyl)-1,2,4,5-tetrazine

被引:5
作者
Maekawa, Masahiko [1 ]
Sugimoto, Kunihisa [2 ]
Okubo, Takashi [3 ]
Kuroda-Sowa, Takayoshi [3 ]
Munakata, Megumu [3 ]
机构
[1] Kinki Univ, Res Inst Sci & Technol, Higashiosaka, Osaka 5778502, Japan
[2] Japan Synchrotron Radiat Res Inst, Res & Utilizat Div, Sayo, Hyogo 6795198, Japan
[3] Kinki Univ, Dept Chem, Higashiosaka, Osaka 5778502, Japan
基金
日本学术振兴会;
关键词
Copper complexes; Tetrazines; Cyclodienes; N ligands; Crystal structures; 1ST CRYSTAL-STRUCTURE; N-DONOR LIGANDS; COORDINATION POLYMERS; ETHYLENE ADDUCTS; 1,5-CYCLOOCTADIENE COD; RADICAL COMPLEX; ANION; 3,6-BIS(2-PYRIDYL)-1,2,4,5-TETRAZINE; SILVER(I); CU(I);
D O I
10.1016/j.ica.2017.08.002
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reactions of CuX2 center dot nH(2)O (X = ClO4, BF4), Cu turnings and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) with excess 1,5-cyclooctadiene (cod) in Me2CO under C2H4 afforded dinuclear Cu(I)-bptz/eta(2), eta(2)-cod-X complexes {(1) and (4)} and dinuclear Cu(I)-2,5-H(2)bptz/eta(2), eta(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 eta(2), eta(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 eta(2), eta(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(BF4)(2)center dot nH(2)O, Cu turnings and bptz with excess 2,5-norbornadiene (nbd) in MeEtCO under C2H4 afforded Cu(I)-2,5-H(2)bptz/eta(2)-nbd-BF4 complex (6). Each Cu(I) atom is coordinated by two chelate N atoms in bptz and one C=C bond in eta(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 eta(2), eta(2)-mode (complexes 1, 2, 4 and 5) while the rigid nbd can produce a Cu (I)-cyclodiene complex in the eta(2)-mode (complex 6). Furthermore, the reaction of Cu(NO3) center dot 3H(2)O, Cu turnings and bptz with excess nbd in Me2CO under C2H4 afforded tetranuclear Cu(I)-4,5-H(2)bptz-NO3 complex (7) containing a unique anionic [Cu-2(nbd)(NO3)(4)](2) moiety. In the cationic [Cu-4(4,5H(2)bptz) 4] 4+ moiety, four Cu(I) atoms are bridged by four 4,5-H(2)bptz ligands to form a [4 x 4] grid-like tetranuclear structure with two 4,5-H(2)bptz ligands lying above the Cu4 mean plane and two lying below. In the anionic [Cu-2(nbd)(NO3)(4)](2) moiety, the two Cu atoms are bridged by one nbd ligand in the mu(2)-eta(2), eta(2)-mode. (C) 2017 Elsevier B. V. All rights reserved.
引用
收藏
页码:204 / 211
页数:8
相关论文
共 59 条
[1]   Olefin coordination in copper(I) complexes of bis(2-pyridyl) amine [J].
Allen, John J. ;
Barron, Andrew R. .
DALTON TRANSACTIONS, 2009, (05) :878-890
[2]   METAL-OLEFIN COMPOUNDS .7. CRYSTAL + MOLECULAR STRUCTURE OF CYCLO-TETRA-MU-CHLORO-TETRAKIS(BICYCLO)2.2.1)HEPTA-2PI,5-DIENECOPPER)I) [J].
BAENZIGER, NC ;
HAIGHT, HL ;
DOYLE, JR .
INORGANIC CHEMISTRY, 1964, 3 (11) :1535-&
[3]   How to circumvent plastic phases: the single crystal X-ray analysis of norbornadiene [J].
Benet-Buchholz, J ;
Haumann, T ;
Boese, R .
CHEMICAL COMMUNICATIONS, 1998, (18) :2003-2004
[4]  
BOEYENS JCA, 1986, S AFR J CHEM, V39, P229
[5]   A spontaneously resolved chiral molecular box:: a cyclic tetranuclear ZnII complex with DPTZ (DPTZ=3,6-di-2-pyridyl-1,2,4,5-tetrazine) [J].
Bu, XH ;
Morishita, H ;
Tanaka, K ;
Biradha, K ;
Furusho, S ;
Shionoya, M .
CHEMICAL COMMUNICATIONS, 2000, (11) :971-972
[6]  
Campos-Fernández CS, 1999, ANGEW CHEM INT EDIT, V38, P3477, DOI 10.1002/(SICI)1521-3773(19991203)38:23<3477::AID-ANIE3477>3.0.CO
[7]  
2-P
[8]   Fine-tuning the ring-size of metallacyclophanes:: A rational approach to molecular pentagons [J].
Campos-Fernández, CS ;
Clérac, R ;
Koomen, JM ;
Russell, DH ;
Dunbar, KR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (04) :773-774
[9]   Anion template effect on the self-assembly and interconversion of metallacyclophanes [J].
Campos-Fernández, CS ;
Schottel, BL ;
Chifotides, HT ;
Bera, JK ;
Bacsa, J ;
Koomen, JM ;
Russell, DH ;
Dunbar, KR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (37) :12909-12923
[10]   Supramolecular architecture of silver(I) coordination polymers containing polydentate N-donor ligands [J].
Chainok, Kittipong ;
Neville, Suzanne M. ;
Forsyth, Craig M. ;
Gee, William J. ;
Murray, Keith S. ;
Batten, Stuart R. .
CRYSTENGCOMM, 2012, 14 (10) :3717-3726