[B(3,5‐C₆H₃Cl₂)₄]^– as a Useful Anion for Organometallic Chemistry

Abstract

Nur Sauerstoff und Säure! Die oxidative Kupplung von Xanthen und anderen aktivierten Benzylverbindungen mit Nukleophilen wie Ketonen benötigt lediglich Sauerstoff und katalytische Mengen an Methansulfonsäure. Lösungsmittel sind nicht erforderlich. Der vorgeschlagene Reaktionsmechanismus umfasst die Substrataktivierung durch Bildung eines Hydroperoxids. Daher kann diese Methode als „autoxidative Kupplungsreaktion“ angesehen werden.

Aza-macrocyclic complexes of the Group 1 cations – synthesis, structures and density functional theory study

“…The VT 133 Cs NMR data for [Cs(Me 6 [18]aneN 6 )][BAr F ] show a singlet at 54.1 ppm (298 K) and this splits into two singlets at 73.3 and 58.7 ppm at 183 K, which we attribute to the slowing of dynamic processes and the presence of two significant stereoisomers ('all up' and alternating 'up-down'). The VT 133 Cs NMR data for [Cs(Me 6 [18]aneN 6 )][BAr F ] show a singlet at 54.1 ppm (298 K) and this splits into two singlets at 73.3 and 58.7 ppm at 183 K, which we attribute to the slowing of dynamic processes and the presence of two significant stereoisomers ('all up' and alternating 'up-down').…”

“…[Na(Me 6 [18] 6 )] + , while structure 2 (D 3d symmetry) has a geometry similar to its K + and Rb + counterparts (vide infra). Structure 1 is more stable than 2 by 28.2 kJ mol −1 in the gas phase (Tables S12, S13, S18 and S19 †).…”

“…The relevant charge densities for the complex cations are shown in Table 1, together with those for Me 6 [18] 6 )] + complex, 5 and 6, are located by the BP86 DFT computations, with structure 5 lower in energy than structure 6 by 43.1 kJ mol −1 (Fig. 9).…”

“…Filtration and removal of solvents affords the thf adduct. 15 Me 6 [18]aneN 6 (Sigma) was used as received. K[BAr F ], Rb[BAr F ], and Cs[BAr F ] were synthesised via cation exchange of Na[BAr F ]·2thf in water at 95°C with excess (5 mol.…”

Reactivity of an Unsaturated Iridium(III) Phosphoramidate Complex, [Cp*Ir{κ2-N,O}][BArF4]

“…We also postulated that these scaffolds might stabilize an unsaturated 16-electron d 6 metal fragment through use of a sterically hindered N-substituent and π-and σ-donation, all requisite features noted by Caulton et al for the preparation of unsaturated Ru(II) piano stool complexes. 4 Only a few examples of phosphoramidate-ligated complexes are known including κ 1 -O-bonded main group complexes of Sn(IV) and Al(III), 17,18 a Ta(V) phosphoramidate complex that has recently been utilized in catalytic room-temperature hydroaminoalkylation, 19 23 for the synthesis of [2] + afforded single crystals of [2][BAr Cl2 4 ] that were suitable for X-ray crystallography. The solid-state structure of [2][BAr Cl2 4 ] shows a two-legged piano stool complex that is formally a 16-electron species, consistent with the NMR spectroscopic data (Figure 1).…”