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Aminoborylene Complexes of Group 6 Elements and Iron: A Synthetic, Structural, and Quantum Chemical Study
Author(s) -
Blank Benoît,
CollingHendelkens Miriam,
Kollann Carsten,
Radacki Krzysztof,
Rais Daniela,
Uttinger Katharina,
Whittell George R.,
Braunschweig Holger
Publication year - 2007
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.200601520
Subject(s) - chemistry , ligand (biochemistry) , metal , transition metal , stereochemistry , population , main group element , crystallography , organic chemistry , catalysis , biochemistry , receptor , demography , sociology
Transition‐metal–borylene complexes of the type [(OC) 5 MBR] {M=Cr, Mo, W; R=N(SiMe 3 ) 2 , 1 a – 3 a , Si(SiMe 3 ) 3 , 4 a } and [(OC) 4 FeBN(SiMe 3 ) 2 ] ( 8 ) were prepared by salt elimination reactions. Synthesis of the latter complex was accompanied by the formation of substantial amounts of an unusual dinuclear iron complex [Fe 2 {μ‐C 2 O 2 (BN(SiMe 3 ) 2 )} 2 (CO) 6 ] ( 9 ). The aminoborylene complexes of Group 6 metals were converted to trans ‐[(Cy 3 P)(CO) 4 MBN(SiMe 3 ) 2 ] ( 5 a – 7 a ) by irradiation in the presence of PCy 3 . Structural and spectroscopic parameters were discussed with respect to the trans ‐effect of the borylene ligand and the degree of MB d π –p π ‐backbonding. Computational studies were performed on Group 6–borylene complexes. The population and topological analyses as well as the molecular orbital composition are consistent with the presence of both σ‐and π‐type interactions. There are, however, indications that the d π –p π ‐backbonding in the silylborylene complex is significantly more pronounced than in the aminoborylene complexes.