Coordination versus coupling of dicyanamide in molybdenum and manganese pyrazole complexes

Inorganic Chemistry
Marta ArroyoFernando Villafañe

Abstract

The reactions of cis-[MoCl(η(3)-methallyl)(CO)(2)(NCMe)(2)] (methallyl = CH(2)C(CH(3))CH(2)) with Na(NCNCN) and pz*H (pzH, pyrazole, or dmpzH, 3,5-dimethylpyrazole) lead to cis-[Mo(η(3)-methallyl)(CO)(2)(pz*H)(μ-NCNCN-κ(2)N,N)](2) (pzH, 1a; dmpzH, 1b), where dicyanamide is coordinated as bridging ligand. Similar reactions with fac-[MnBr(CO)(3)(NCMe)(2)] lead to the pyrazolylamidino complexes fac-[Mn(pz*H)(CO)(3)(NH═C(pz*)NCN-κ(2)N,N)] (pzH, 2a; dmpzH, 2b), resulting from the coupling of pyrazol with one of the CN bonds of dicyanamide. The second CN bond of dicyanamide in 2a undergoes a second coupling with pyrazole after addition of 1 equiv of fac-[MnBr(CO)(3)(pzH)(2)], yielding the dinuclear doubly coupled complex [{fac-Mn(pzH)(CO)(3)}(2)(μ-NH═C(pz)NC(pz)=NH-κ(4)N,N,N,N)]Br (3). The crystal structure of 3 reveals the presence of two isomers, cis or trans, depending on whether the terminal pyrazoles are coordinated at the same or at different sides of the approximate plane defined by the bridging bis-amidine ligand. Only the cis isomer is detected in the crystal structure of the perchlorate salt of the same bimetallic cation (4), obtained by metathesis with AgClO(4). All the N-bound hydrogen atoms of the cations in 3 or 4 are i...Continue Reading

References

May 9, 2002·Chemical Reviews·Vadim Yu Kukushkin, Armando J L Pombeiro
Dec 20, 2002·Angewandte Chemie·Thomas Steiner
Jul 5, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Erwin ReisnerBernhard K Keppler
Jan 24, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Bin DingHong-Gen Wang
Aug 2, 2006·Inorganic Chemistry·Asako Igashira-KamiyamaTasuku Ito
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Sep 22, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Paloma ParedesFernando Villafañe

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Citations

Sep 22, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Patricia Gómez-IglesiasFernando Villafañe
Sep 26, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Patricia Gómez-IglesiasFernando Villafañe
Jan 24, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Marta ArroyoFernando Villafañe
Nov 8, 2014·Inorganic Chemistry·Patricia Gómez-IglesiasFernando Villafañe

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