B(C6F5)3 adducts of transition metal acyl compounds

Abstract

The transition metal acyl compounds [Co(L)(CO)3(COMe)] (L = PMe3, PPhMe2, P(4-Me-C6H4)3, PPh3 and P(4-F-C6H4)3), [Mn(CO)5(COMe)] and [Mo(PPh3)(eta(5)-C5H5)(CO)2(COMe)] react with B(C6F5)3 to form the adducts [Co(L)(CO)3(C{OB(C6F5)3}Me)] (L = PMe3, 1, PPhMe2, 2, P(4-Me-C6H4)3, 3, PPh3, 4, P(4-F-C6H4)3), 5, [Mn(CO)5(C{OB(C6F5)3}Me)] 6 and [Mo(eta(5)-C5H5)(PPh3)(CO)2(C{OB(C6F5)3}Me)], 7. Addition of B(C6F5)3 to a cooled solution of [Mo(eta(5)-C5H5)(CO)3(Me)], under an atmosphere of CO gave [Mo(eta(5)-C5H5)(CO)3(C{OB(C6F5)3}Me)] 8. In the presence of adventitious water, the compound [Co{HOB(C6F5)3}2{OP(4-F-C6H4)3}2] 9, was formed from [Co(P(4-F-C6H4)3)(CO)3(C{OB(C6F5)3}Me)]. The compounds 4 and 9 have been structurally characterised. The use of B(C6F5)3 as a catalyst for the CO-induced migratory-insertion reaction in the transition metal alkyl compounds [Co(PPh3)(CO)3(Me)], [Mn(CO)5(Me)], [Mo(eta(5)-C5H5)(CO)3(Me)] and [Fe(eta(5)-C5H5)(CO)2(Me)] has been investigated.

Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal‐free Hydrogenation of Alkenes

“…At 40 ppm in the 11 B NMR spectrum of the wetted BCF‐impregnated polyamine there is an additional small peak. The BCF itself has a chemical shift of 65–59 ppm (in CD 2 Cl 2 /C 6 D 6 , CD 2 Cl 2 , C 6 D 6 , CDCl 3 ) . Because of this, it is hypothesized that this signal results from the appearance of a borane species with less interaction with the polymer when the solvent is added.…”

Reaction of a 6‐Dimethylaminopentafulvene with the Mes2PCH2CH2B(C6F5)2 Frustrated Lewis Pair

“…The 11 B{ 1 H} NMR signal is relatively sharp and in a range as expected for fourcoordinate boron, formed by internal N À B interaction ( 11 B{ 1 H}: d = + + 4.6 ppm). [13,14] The carbocyclic five-mem- (d, 3 J P-C = 15.3 Hz)), respectively. The X-ray crystal structure analysis of 9 (see Figure 1) confirms that the B À C s bond of the reagent 1 was cleaved during the reaction and that the resulting À BA C H T U N G T R E N N U N G (C 6 F 5 ) 2 and À CH 2 CH 2 À PMes 2 components were added to the adjacent former fulvene ring carbon atoms (C1 and C8, see Figure 1).…”

“…X-ray crystal structure analysis of 13: Formula C 21 H14 BF 10 N, M = 481.14, light yellow crystal 0.17 0.15 0.15 mm, a = 15.1034(3), b = 15.6593(4), c = 16.4607(4) , V = 3893.10(16) 3 , 1 calc = 1.642 g cm À3 , m = 1.457 mm À1 , empirical absorption correction (0.790 T 0.811), Z = 8, orthorhombic, space group Pbca (No. 61), l = 1.54178 , T = 223(2) K, w and f scans, 27 558 reflections collected (AE h, AE k, AE l), [(sinq)/l] = 0.60 À1 , 3376 independent (R int = 0.093) and 2342 observed reflections [I !…”

Boron, aluminium, gallium, indium and thallium

“…The use of B(C 6 F 5 ) 3 as a catalyst for CO induced migratory insertion has also been reported. 71 The stereochemistry of mono-and bis-B(C 6 F 5 ) 3 -benzotriazole adducts have been investigated by variable temperature 19 F-NMR spectroscopy and X-ray crystallography. 72 The reaction of B(C 6 F 5 ) 3 with 7-azaindole has been investigated, and the competitive coordination of the azaindole, pyrole and indole adducts with pyridine investigated using NMR spectroscopy.…”

“…197 The possibility that the general lack of common octahedral Ga hydride structures might be a property endemic to gallium itself, was considered. 198 A helpful study describing the solid-state NMR characteristics of both 69 Ga and 71 Ga was reported. 199 Two binary compounds, Rh 4 Ga 21 and Rh 3 Ga 16 , represent new structure types for intermetallic compounds, and are best described using the intergrowth structure concept.…”