Neue Wege zu Bis[(cyclopentadienyl)cobalt]‐μ‐(η⁵‐2,3‐dihydro‐1,3‐diborolyl)‐Tripeldeckerkomplexen über Wasserstoff‐Verschiebungsreaktionen in Derivaten des 4,5‐Diisopropyliden‐1,3‐diborolans, des 2,4,5‐Triisopropyliden‐1,3‐diborolans und des Benzo‐1,3‐diborafulvens

Abstract

New Routes to Bis[(cyclopentadienyl)cobalt]-~-(~5-2

Synthesis of μ-Diborolyl Triple-Decker Complexes by Electrophilic Stacking. Similar Bonding Properties of Anions [CpCo(1,3-C3B2H5)]− and Cp− toward Transition Metals

“… c From ref 55 d From ref 7 e BP86/6-311G(d,p) for C, H, and B and LANL2DZ for Co and Ru. f BP86/6-311G(d,p) for C, H, and B and def2-TZVP for Co and Ru. g BP86/def-TZVP. h BP86/TZ2P. …”

“…For instance, stacking of 2 with CpFe(cod) (cod = 1,5-cyclooctadiene) yields the diamagnetic 30 valence electron (VE) iron−cobalt triple-decker complexes CpCo(μ-1,3-C 3 B 2 R 5 )FeCp, and the reaction of CpNi(1,3-C 3 B 2 R 5 ) with CpCoL 2 (L = CO, C 2 H 4 ) gives paramagnetic 32 VE cobalt−nickel analogues CpCo(μ-1,3-C 3 B 2 R 5 )NiCp . The anionic sandwich complexes 3 (obtained by deprotonation of 2 ) , react with metal halides, leading to tetra-decker complexes CpCo(μ-1,3-C 3 B 2 R 5 )M(μ-1,3-C 3 B 2 R 5 )CoCp (M = Cr, Mn, Fe, Co, Ni, Zn, and Sn) . Three-component reaction of anion 3 , dianion [7,8-C 2 B 9 H 11 ] 2− , and CoCl 2 gives the metallacarborane triple-decker complex CpCo(μ-1,3-C 3 B 2 R 5 )Co(C 2 B 9 H 11 ) .…”

Isolation of Free Phenylide-like Carbanions with N-Heterocyclic Carbene Frameworks

“…The ionic precursors 1 were prepared cleanly and in high yield via the ring-closing reaction of silylated bis(2,6-diisopropylphenyl)formamidine with 1,1-bis(organochloroboryl)ethane in the presence of Me 3 SiOTf, as described for imidazolium analogs incorporating inorganic backbones. , The phenyl derivative MeCH(PhBCl) 2 was synthesized through the metathesis reaction of 1,1-MeCH(BCl 2 ) 2 with SnPh 4 , while MeCH(Me 2 NBCl) 2 was obtained via the reaction of MeCH(BCl 2 ) 2 with Me 3 SiNMe 2 . The 1 H NMR spectrum of 1c displayed the resonances expected for a solvent-separated ion pair with C s symmetry of the cation, as observed for 1a .…”

“…The solvents were dried and deoxygenated prior to use. Derivatives 1a − 3a , as well as MeCH(RBCl) 2 (R = Ph, Me 2 N) , and (2,6- i Pr 2 C 6 H 3 )NCH−N(SiMe 3 )(2,6- i Pr 2 C 6 H 3 ), were prepared according to literature procedures. All NMR spectra were run on a Bruker Avance DRX-400 instrument and chemical shifts are reported in δ units (ppm) using the solvent as an internal reference: C 6 D 6 H (7.15 ppm, 1 H) and C 6 D 6 (128.0 ppm, 13 C); THF- d 7 (3.58 ppm, 1 H) and THF- d 8 (67.57 ppm, 13 C).…”