Boryl- and Bridging Boryleneiron Complexes from Aminodichloroboranes

Abstract

Depending on the nature of the amino group bound to the boron atom, the reactions of various aminodichloroboranes R2NBCl2 with Na[(η5‐C5R′5)Fe(CO)2] yield either boryl or bridging borylene complexes of iron. The compounds [(C5R′5)(CO)2Fe{BCl(NR2)}] (1a, C5R′5 = C5H5, R = Me; 1b, C5R′5 = C5H4Me, R = Me; 1c, C5R′5 = C5Me5, R = Me) and [(η‐BNR2)(μ‐CO){(C5R′5)Fe(CO)}2] (2a, C5R′5 = C5H5, R = SiMe3; 2b, C5R′5 = C5H4Me, R = SiMe3) were isolated as orange (1a−c) or red (2a, b) crystalline solids, and characterized by multinuclear NMR methods and IR spectroscopy. The structures of 1c and 2b in the crystalline state were determined by single‐crystal X‐ray studies.

Structural characterization of the anionic halfsandwich complex and its reactivity towards stannanes and distannanes

“…The outstanding preparative versatility of this route has led to a vast range of organometallic species so far, most of which have been obtained from group 13 [4][5][6][7][8][9][10][11][12][13][14][15] and group 14 precursors [16][17][18][19][20].…”

“…The molecule shows a four-legged piano-stool geometry with a large Mo-Sn distance of 2.8546(3) Å which is comparable to that of related molybdenum stannyl complexes such as ½fFeðg 5 -C 5 H 5 ÞðCOÞ 2 g 2 fMoðg 5 -C 5 H 5 ÞðCOÞ 3 gSnCl [22]. The SnMe 3 ligand adopts a staggered conformation with respect to the ½Moðg 5 -C 5 H 5 ÞðCOÞ 3 fragment as indicated by a dihedral angle Cp Cent -Mo-Sn-C6 of 175.39°.This orientation together with the large Mo-Sn separation allows for rather acute Sn-Mo-C(O) angles of 68.48(6) and 69.42 (8)°compared to the (O)C-Mo-C(O) angles of (79.30 (9) and 81.18(9)°). The coordination sphere around the tin atom displays angles from 106.97(7) to 112.40(7)°, whereby the small deviation from the ideal tetrahedral geometry is presumably caused by packing effects within the unit cell (see Fig.…”

Rhabdomyosarcoma in infants younger than one year old

“…The Fe1B1 and Fe2B2 bond lengths are 1.98(2) and 1.842(12) Å, respectively. These are considerably shorter than that found in the boryl complex [CpFe(CO) 2 BPh 2 ] (2.034(3) Å)46 and bridged borylene complex [(η‐BN(SiMe 3 ) 2 )(μ‐CO){Cp + Fe(CO)} 2 ] (2.007(3) and 2.002(3) Å) (Cp + =(η 5 ‐C 5 H 4 Me)) 47…”

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…This same research group prepared [202] amino-substituted boryl complexes of Fp by reacting dimethyl aminodichloroborane and di(trimethylsilyl)aminodiborane with the Fp anion To study if the ferrocenyl(bromo)boryl group could serve as a probe for the presence of any significant Fe-B -bonding, Braunschweig and coworkers synthesized and characterized Fp[B(Fc)Br] (Scheme 142) [206]. By comparing the crystal structure of this complex and its Fp* (C 5 Me 5 Fe(CO) 2 ) analog, these researchers concluded that the differences in steric bulk of the 5 -C 5 R 5 (R = H or Me) in the Fp ligands, affects the orientation and thus its -bonding.…”