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Reactions of 1,3,2‐Diselenaphospholanes with Lewis Acids: Borane and (Pentamethylcyclopentadienyl)rhodium and ‐iridium Dichloride
Author(s) -
Wrackmeyer Bernd,
Klimkina Elena V.,
Milius Wolfgang
Publication year - 2014
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.201402486
Subject(s) - chemistry , borane , iridium , rhodium , adduct , lewis acids and bases , medicinal chemistry , ring (chemistry) , boranes , ligand (biochemistry) , nuclear magnetic resonance spectroscopy , boron , crystallography , stereochemistry , catalysis , organic chemistry , biochemistry , receptor
2‐R‐1,3,2‐Diselenaphospholanes (R = i Pr, Ph) with an annelated 1,2‐dicarba‐ closo ‐dodecaborane(12) unit were treated with Lewis acids such as borane reagents (BH 3 in THF, and BH 3 –SMe 2 ) as well as Cp*‐rhodium and ‐iridium dichloride (Cp* = pentamethylcyclopentadienyl). In all cases, the adduct formation in the beginning was followed by ring expansion through insertion of the borane or Cp*MCl 2 into one of the P–Se bonds accompanied by transfer of a hydrido or chlorido ligand to phosphorus. Finally, the P–R unit was displaced from the ring to give the exchange products, in which the boron or the metal had become part of the five‐membered rings. The reactions were monitored by NMR spectroscopy ( 1 H, 11 B, 13 C, 31 P, and 77 Se). The proposed reaction sequences were found to be in agreement with calculated [B3LYP/6‐311+G(d,p), LANL2DZ (Rh, Ir) level of theory] relative energies of optimized gas‐phase structures of the various products. The novel molecular structure of the preferred insertion product with M = Ir, R = i Pr was determined by X‐ray analysis.