Document Detail


Structural diversity among copper(i) ethylene adducts of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine.
MedLine Citation:
PMID:  23340488     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The reaction of Cu(ClO(4))·6H(2)O, Cu turnings, and 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) in Me(2)CO under C(2)H(4) afforded brownish-red needle crystals of {[Cu(2)(bptz˙(-))(C(2)H(4))(2)](ClO(4))}(2) () as a minor product and brown plate crystals of [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](ClO(4))(2)·2Me(2)CO (). The X-ray crystallographic study showed that complex is composed of two independent [Cu(2)(bptz˙(-))(C(2)H(4))(2)](+) cation moieties and two ClO(4)(-) anions. In both of the cation moieties, each Cu(i) atom is coordinated by two chelate N atoms of bptz˙(-) and the C[double bond, length as m-dash]C bond of C(2)H(4) in the trigonal-planar geometry to form a unique transoid dinuclear Cu(i)-bptz˙(-)/C(2)H(4) adduct bearing a metal-stabilized tetrazine anion radical, bptz˙(-), which was produced by the one-electron reduction of bptz. In contrast, complex consists of one [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moiety, two ClO(4)(-) anions, and two solvated Me(2)CO molecules. Each Cu(i) atom is coordinated by two chelate N atoms of 2,5-H(2)bptz and the C[double bond, length as m-dash]C bond of C(2)H(4) in the trigonal-planar geometry to afford a transoid dinuclear Cu(i)-C(2)H(4) adduct with 2,5-H(2)bptz, which was produced by the two-electron reduction of bptz. Additionally, the similar reaction of Cu(ClO(4))·6H(2)O, Cu turnings, and bptz in Me(2)CO or MeEtCO under C(2)H(4) in the presence of ferrocene afforded orange brick crystals of [Cu(2)(bpdpyz)(C(2)H(4))(2)](ClO(4))(2)·Me(2)CO () and [Cu(2)(bpdpyz)(C(2)H(4))(2)](ClO(4))(2) (), respectively, together with complex in higher yield. This result shows that 3,6-bis(2-pyridyl)-4,5-dihydropyridazine (bpdpyz) was produced by the cycloaddition of bptz with C(2)H(4)via a Diels-Alder addition and retro-Diels-Alder elimination of dinitrogen. In complexes and , each Cu(i) atom is coordinated by two chelate N atoms of bpdpyz and the C[double bond, length as m-dash]C bond of C(2)H(4) to afford an unusual cisoid dinuclear Cu(i)-C(2)H(4) adduct. Further attempts to react excess [Cu(C(2)H(4))(n)]ClO(4) with bptz in Me(2)CO under C(2)H(4) afforded black brick crystals of [Cu(4)(4,5-H(2)bptz)(4)](ClO(4))(4)·2Me(2)CO () together with complex . Complex is the first [4 × 4] grid-like tetranuclear Cu(i) complex constructed by the combination of Cu(i) ion and 4,5-H(2)bptz. The four Cu(i) atoms are spanned by four 4,5-H(2)bptz ligands, with two lying above the Cu(4) mean plane and two lying below. In contrast, the similar reaction of excess [Cu(C(2)H(4))(n)]ClO(4) with bptz in Me(2)CO under C(2)H(4) in the presence of ferrocene afforded reddish-brown brick crystals of {[Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](ClO(4))(2)}(2)·Me(2)CO () together with complexes and . Complex is composed of two independent [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moieties, four ClO(4)(-) anions, and a solvated Me(2)CO molecule. It is interesting that the structures of the two [Cu(2)(2,5-H(2)bptz)(C(2)H(4))(2)](2+) cation moieties are different: one has a nearly planar structure and the other possesses a boat conformation owing to the bent central dihydrotetrazine ring.
Authors:
Masahiko Maekawa; Takeshi Miyazaki; Kunihisa Sugimoto; Takashi Okubo; Takayoshi Kuroda-Sowa; Megumu Munakata; Susumu Kitagawa
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-23
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Research Institute for Science and Technology, Kinki University, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan. maekawa@rist.kindai.ac.jp.
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