Octahedral manganese(i) and ruthenium(ii) complexes containing 2-(methylamido)pyridine-borane as a tripod Kappa 3N,H,H-ligand

The borane adduct of the 2-(methylamido)pyridine anion, [mapyBH3]-, has been incorporated into octahedral metal complexes. In fac-[Mn( Kappa 3N,H,H-mapyBH3)(CO)3] (1) and fac-[RuH( Kappa 3N,H,H-mapyBH3)(CO)(PiPr3)] (2), which have been prepared by treating K[mapyBH3] with fac-[MnBr(MeCN)2(CO)3] and...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2017-03, Vol.46 (12), p.4009-4017
Main Authors: Brugos, Javier, Cabeza, Javier A, Garcia-Alvarez, Pablo, Perez-Carreno, Enrique, Van der Maelen, Juan F
Format: Article
Language:English
Subjects:
Anions
Bonding
Boranes
Chemical bonds
Hydrides
Ligands
Tripods
X ray diffraction
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Summary:The borane adduct of the 2-(methylamido)pyridine anion, [mapyBH3]-, has been incorporated into octahedral metal complexes. In fac-[Mn( Kappa 3N,H,H-mapyBH3)(CO)3] (1) and fac-[RuH( Kappa 3N,H,H-mapyBH3)(CO)(PiPr3)] (2), which have been prepared by treating K[mapyBH3] with fac-[MnBr(MeCN)2(CO)3] and [RuHCl(CO)(PiPr3)2], respectively, it behaves as a tripod ligand, attached to the metal atom through the amido N atom and through two H atoms of the BH3 moiety. X-ray diffraction analyses and theoretical studies (DFT, QTAIM) have shown that the MH2B atom grouping of 1 and 2 comprises two 3c-2e M-H-B interactions that are between those of the Shimoi type ( Kappa 1H coordination of the B-H bond) and those of the agostic type ( Kappa 2B,H coordination of the B-H bond). However, while both M-H-B interactions are almost identical in complex 1, this is not the case in complex 2, in which one M-H-B interaction is more agostic than the other due to the different trans influence of the hydride and phosphane ligands.
ISSN:1477-9226
1477-9234
DOI:10.1039/c7dt00378a