Reactions of a BICAAC with hydroboranes: propensity for Lewis adduct formation and carbene insertion into the B-H bond

The reactivity of a bicyclic (alkyl)(amino)carbene (BICAAC) towards different boranes has been examined in the present work. The reactions with boranes BX 3 ·SMe 2 (X = H, Cl, Br), BF 3 ·OEt 2 and BCl 3 yield Lewis adducts [BICAAC·BH 3 ] ( 1 ), [BICAAC·BHCl 2 ] ( 2 ), [BICAAC·BH 2 Cl] ( 3 ), [BICAAC...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2019-12, Vol.48 (47), p.17472-17478
Main Authors: Manar, Krishna K, Porwal, Vishal Kumar, Kamte, Rohit S, Adhikari, Manu, Thakur, Sandeep Kumar, Bawari, Deependra, Choudhury, Angshuman Roy, Singh, Sanjay
Format: Article
Language:English
Subjects:
Adducts
Boranes
Boron chlorides
Boron compounds
Crystallography
Hydrogen bonds
Infrared spectroscopy
Insertion
NMR spectroscopy
Single crystals
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Summary:The reactivity of a bicyclic (alkyl)(amino)carbene (BICAAC) towards different boranes has been examined in the present work. The reactions with boranes BX 3 ·SMe 2 (X = H, Cl, Br), BF 3 ·OEt 2 and BCl 3 yield Lewis adducts [BICAAC·BH 3 ] ( 1 ), [BICAAC·BHCl 2 ] ( 2 ), [BICAAC·BH 2 Cl] ( 3 ), [BICAAC·BF 3 ] ( 4 ), [BICAAC·BCl 3 ] ( 5 ) and [BICAAC·BBr 3 ] ( 6 ) respectively, whereas more hydridic boranes, 9-borabicyclo[3.3.1]nonane (9-BBN) and catecholborane (HBcat), enable the insertion of the carbene carbon into the B-H bond to form [BICAAC(H)-(9-BBN)] ( 7 ) and [BICAAC(H)-Bcat] ( 8 ). These complexes are the first examples of BICAAC-boron compounds and have been characterized using IR, multinuclear NMR spectroscopy, HRMS spectrometry and single crystal X-ray diffraction. Computational analyses were also performed to gain insight into the mechanism of B-H bond activation and adduct formation. Furthermore, the reactions of the BICAAC with boranes have been compared with the known reactions of CAACs and NHCs. A BICAAC interacts differently with different boranes: Lewis adducts were formed with simple hydroboranes and insertion of the carbene carbon into the B-H bond was observed with more hydridic boranes.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03382c