Synthesis and Dimer Cleavage Reactions of the N(2)S Thiolate Bridged Dimer [(mmp-dach)(2)Ni(2)]Cl(2). Academic Article

abstract

• The facile synthesis of a monoderivatized N(2)S ligand based on the cyclic diamine diazacycloheptane provides a tridentate donor which coordinates nickel(II), yielding a dithiolate bridged nickel dimer with a hinge angle of 135.7 degrees and acute N-Ni-N bite angles of ca. 80 degrees. Dimer splitting occurs on reaction with iodoacetamide, producing an S-alkylated octahedral complex. Cyanide also cleaves the dimer, resulting in a cyanide-bound N(2)S square planar monomer with two nucleophilic sites, thiolate-S and cyanide-N. Molecular structures of the dimeric cation, [(mmp-dach)(2)Ni(2)]Cl(2), the iodoacetamide derivative, [(dtp-dach)Ni(MeCN)(2)]Cl(2), and an S-oxygenate, [(smp-dach)Ni(CN)], are reported.

authors

• Darensbourg, Marcetta

published proceedings

• Inorg Chem

author list (cited authors)

• Grapperhaus, C. A., Bellefeuille, J. A., Reibenspies, J. H., & Darensbourg, M. Y.

citation count

• 15

complete list of authors

• Grapperhaus, Craig A||Bellefeuille, John A||Reibenspies, Joseph H||Darensbourg, Marcetta Y

publication date

• August 1999

publisher

• American Chemical Society (ACS)  Publisher

published in

• Inorganic Chemistry  Journal

keywords

• 0306 Physical Chemistry (incl. Structural)

PubMed Central ID

• 11671129

Digital Object Identifier (DOI)

• 10.1021/ic990106z

start page

• 3698

end page

• 3703

volume

• 38

issue

• 16

URL

• http%3A%2F%2Fdx.doi.org%2F10.1021%2Fic990106z