Premium
Heterolytic Si−H Bond Cleavage at a Molybdenum‐Oxido‐Based Lewis Pair
Author(s) -
Zwettler Niklas,
Walg Simon P.,
Belaj Ferdinand,
MöschZanetti Nadia C.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800226
Subject(s) - chemistry , heterolysis , adduct , molybdenum , lewis acids and bases , benzaldehyde , reactivity (psychology) , borane , bond cleavage , medicinal chemistry , frustrated lewis pair , stereochemistry , cationic polymerization , electrophile , crystallography , polymer chemistry , inorganic chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C 6 F 5 ) 3 gave access to the Lewis adduct [Mo{OB(C 6 F 5 ) 3 }(N t Bu)L 2 ] featuring reversible B−O bonding in solution. The resulting frustrated Lewis pair (FLP)‐like reactivity is reflected by the compound's ability to heterolytically cleave Si−H bonds, leading to a clean formation of the novel cationic Mo VI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR 3 )(N t Bu)L 2 ][HB(C 6 F 5 ) 3 ]. These compounds possess properties highly unusual for molybdenum d 0 species such as an intensive, charge‐transfer‐based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single‐crystal X‐ray diffraction analyses of 2 and 4 b , a derivative of 3 b featuring the [FB(C 6 F 5 ) 3 ] − anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B−H bond of the borohydride anion.