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Paramagnetic (1,3‐Diborolyl)ruthenium Triple‐Decker Complexes and Transformation into Diamagnetic Complexes Having Bridging 1,3‐Diborafulvene Ligands
Author(s) -
Mutseneck Elena V.,
Wadepohl Hubert,
Enders Markus,
Kudinov Alexander R.,
Siebert Walter
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200901232
Subject(s) - chemistry , ruthenium , crystallography , diamagnetism , paramagnetism , stereochemistry , crystal structure , catalysis , physics , quantum mechanics , magnetic field , biochemistry
The paramagnetic triple‐decker complexes [(Cp*Ru) 2 {μ‐(CMe) 3 (BCl)(BMe)}] ( 3b ) and [(Cp*Ru) 2 {μ‐(CMe) 3 (BCl) 2 }] ( 3c ) are formed by refluxing a mixture of [Cp*RuCl] 4 and pentamethyl‐2,3‐dihydro‐1,3‐diborole in thf. In CH 2 Cl 2 under air complex 3b slowly looses a hydrogen atom with formation of the diamagnetic triple‐decker [(Cp*Ru) 2 {μ‐η 5 :η 6 ‐(CMe) 3 (BCl)(BCH 2 )}] ( 4b ) with the unsymmetrical dihydrodiborafulvene derivative in a bridging position. The analogous complex [(Cp*Ru) 2 {μ‐η 5 :η 6 ‐(CMe) 3 (BMe)‐(BCH 2 )}] ( 4a ) is obtained by interaction of HCl with the triple‐decker [(Cp*Ru) 2 {μ‐(CMe) 3 (BMe) 2 }] ( 3a ). According to calculations, complexes 4a and 4b have an almost non‐distorted triple‐decker arrangement with a strong bending of the B=CH 2 group toward one of the Ru atoms. For the formation of 3b and 3c the chloro‐containing sandwich complexes [Cp*Ru{η 5 ‐(CMe) 3 (BCl)(BR 1 )}] ( 2b , c ; R 1 = Me, Cl) are proposed as intermediates. The constitutions of the complexes are derived from NMR, MS and DFT data, and the molecular structure of 3b is confirmed by an X‐ray diffraction analysis.