Document Detail

Synthesis of binucleating macrocycles and their nickel(II) hydroxo- and cyano-bridged complexes with divalent ions: anatomical variation of ligand features.
MedLine Citation:
PMID:  23030366     Owner:  NLM     Status:  MEDLINE    
The planar NNN-pincer complexes [M(II)(pyN(2)(Me2))(OH)](1-) (M(II) = Ni, Cu) fix CO(2) in η(1)-OCO(2)H complexes; results for the copper system are described. Mn(II), Fe(II), Co(II), and Zn(II) behave differently, forming [M(II)(pyN(2)(Me2))(2)](2-) with N(4)O(2) coordination. Incorporation of the Ni(II) pincer into binucleating macrocycle 2 containing a triamino M(II) locus connected by two 1,3-biphenylene groups affords proximal Ni(II) and M(II) sites for investigation of the synthesis, structure, and reactivity of Ni-X-M bridge units. This ligand structure is taken as a reference for variations in M(II) atoms and binding sites and bridges X = OH(-) and CN(-) to produce additional members of the macrocyclic family with improved properties. Macrocycle 2 with a 22-membered ring is shown to bind M(II) = Mn, Fe, and Cu with hydroxo bridges. Introduction of the 4-Bu(i)O group (macrocycle 3) improves the solubility of neutral complexes such as those with Ni(II)-OH-Cu(II) and Ni(II)-CN-Fe(II) bridges. Syntheses of macrocycle 5 with a 7-Me-[12]aneSN(3) and macrocycle 6 with a 1,8-Me(2)-[14]aneN(4) M(II) binding site are described together with hydoxo-bridged Ni/Cu and cyano-bridged Ni/Fe complexes. This work was motivated by the presence of a Ni···(HO)-Fe bridge grouping in a reactive state of carbon monoxide dehydrogenase. Attempted decrease in Ni-(OH)-M distances (3.70-3.87 Å) to smaller values observed in the enzyme by use of macrocycle 4 having 1,2-biphenylene connectors led to a mononuclear octahedral Ni(II) complex. Bridge structural units are summarized, and the structures of 14 macrocyclic complexes including 8 with bridges are described.
Xiaofeng Zhang; Deguang Huang; Yu-Sheng Chen; R H Holm
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, U.S. Gov't, Non-P.H.S.     Date:  2012-10-03
Journal Detail:
Title:  Inorganic chemistry     Volume:  51     ISSN:  1520-510X     ISO Abbreviation:  Inorg Chem     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-15     Completed Date:  2013-02-28     Revised Date:  2013-10-17    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  11017-29     Citation Subset:  IM    
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
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MeSH Terms
Chemistry Techniques, Synthetic
Macrocyclic Compounds / chemistry*
Models, Molecular
Molecular Conformation
Nickel / chemistry*
Nitriles / chemistry*
Organometallic Compounds / chemical synthesis*,  chemistry*
Grant Support
Reg. No./Substance:
0/Ligands; 0/Macrocyclic Compounds; 0/Nitriles; 0/Organometallic Compounds; 7440-02-0/Nickel

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