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Article: Formation and crystallographic elucidation of stable [4 + 2]-coordinate nickel(ii) N,S-heterocyclic carbene (NSHC) complexes

TitleFormation and crystallographic elucidation of stable [4 + 2]-coordinate nickel(ii) N,S-heterocyclic carbene (NSHC) complexes
Authors
Issue Date2009
Citation
Dalton Transactions, 2009, n. 10, p. 1853-1858 How to Cite?
AbstractA series of square-planar N,S-heterocyclic carbene (NSHC) complexes trans-[NiX2(N-RBzTh)2] (BzTh = benzothiazolin-2-ylidene) (R/X = Bz/Br; Me/I; Et/I; Pri/I; Bui/I) have been synthesized and characterized by X-ray single-crystal diffraction analysis. These are the first crystallographically established NSHC complexes of nickel in the literature. The N,S-heterocyclic carbene (NSHC) rings invariably twist away from co-planarity with the metal coordination plane such that the N-substituent moves on top and below the metal to facilitate electrostatic γ-hydride interaction, thus giving an essentially [4 + 2] coordination at the Ni(ii) center. These compounds are active toward reductive Ullmann-type coupling reactions in Bu4NBr showing higher activities towards bromoanisole or bromotoluene than bromobenzene. The complex trans-[NiI2(N-Pr iBzTh)2] with the shortest Ni⋯H anagostic separation and a near-ideal orthogonal orientation between the carbene and metal planes gives the highest yields. © 2009 The Royal Society of Chemistry.
Persistent Identifierhttp://hdl.handle.net/10722/219597
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404

 

DC FieldValueLanguage
dc.contributor.authorDing, Nini-
dc.contributor.authorZhang, Jun-
dc.contributor.authorHor, T. S Andy-
dc.date.accessioned2015-09-23T02:57:29Z-
dc.date.available2015-09-23T02:57:29Z-
dc.date.issued2009-
dc.identifier.citationDalton Transactions, 2009, n. 10, p. 1853-1858-
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10722/219597-
dc.description.abstractA series of square-planar N,S-heterocyclic carbene (NSHC) complexes trans-[NiX2(N-RBzTh)2] (BzTh = benzothiazolin-2-ylidene) (R/X = Bz/Br; Me/I; Et/I; Pri/I; Bui/I) have been synthesized and characterized by X-ray single-crystal diffraction analysis. These are the first crystallographically established NSHC complexes of nickel in the literature. The N,S-heterocyclic carbene (NSHC) rings invariably twist away from co-planarity with the metal coordination plane such that the N-substituent moves on top and below the metal to facilitate electrostatic γ-hydride interaction, thus giving an essentially [4 + 2] coordination at the Ni(ii) center. These compounds are active toward reductive Ullmann-type coupling reactions in Bu4NBr showing higher activities towards bromoanisole or bromotoluene than bromobenzene. The complex trans-[NiI2(N-Pr iBzTh)2] with the shortest Ni⋯H anagostic separation and a near-ideal orthogonal orientation between the carbene and metal planes gives the highest yields. © 2009 The Royal Society of Chemistry.-
dc.languageeng-
dc.relation.ispartofDalton Transactions-
dc.titleFormation and crystallographic elucidation of stable [4 + 2]-coordinate nickel(ii) N,S-heterocyclic carbene (NSHC) complexes-
dc.typeArticle-
dc.description.natureLink_to_subscribed_fulltext-
dc.identifier.doi10.1039/b815876b-
dc.identifier.scopuseid_2-s2.0-61349107461-
dc.identifier.issue10-
dc.identifier.spage1853-
dc.identifier.epage1858-
dc.identifier.eissn1477-9234-

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