Iron pentacarbonyl ligands on silver scorpionates

Abstract

Fluorinated tris(pyrazolyl)borate supporting ligands enable the stabilization of silver(I) bonded to a neutral, organometallic Fe(CO)5 ligand. The Ag-Fe interaction in these molecules is mainly electrostatic in nature, but σ-donor and...

Towards clustered carbonyl cations [M3(CO)14]2+ (M = Ru, Os): the need for innocent deelectronation

“…The formation of adducts of TMCs with silver( i ) cations has already been observed by our group 28,38 with recent additions from the Dias group. 39,40 These complexes can be seen as metal-only Lewis pairs (MOLPs). 41 While zero valent and pentacoordinated group 8 complexes are known for having Lewis-basic behaviour and silver cations are known to be Lewis acidic, their heterodinuclear complexes are scarce.…”

Exploring opportunities for tuning phenyltris(pyrazol-1-yl)borate donation by varying the extent of phenyl substituent fluorination

“…11 B NMR (128 MHz, CD 3 CN): δ −0.77 (s). 19 F{ 1 H} NMR (376 MHz, CD 3 CN): δ −137.3 (d, 3 J FF = 19.7 Hz, m-F), −164.1 (t, 3 J FF = 19.7 Hz, p-F). 1 H NMR (400 MHz, CD 3 CN): δ 7.82 (m, 3H, pzH-3/-5), 7.62 (m, 2H, o-H), 7.47 (d, J = 2.4 Hz, 3H, pz-3/-5), 6.12 (app.…”

“…t, J = 2.2 Hz, 3H, pzH-4), 3.11 (m, 8H, Et 4 N), 1.17 (m, 12H, Et 4 N). 13 C{ 1 H} NMR (101 MHz, CD 3 CN): δ 231.8 (s, CO), 151.9 (dd, 1 J CF = 251 Hz, 2 J CF = 6.1 Hz, m-C), 145.1 (s, pzC-3/-5), 140.4 (dt, 1 J CF = 251 Hz, 2 J CF = 15.4 Hz, p-F), 135.9 (s, pzC-3/-5), 120.0 (dd, 2 J CF = 14.6 Hz, 3 A 1.00 mL stock solution of 2-methylallyl bromide (0.230 g, 1.70 mmol) in CH 2 Cl 2 was added to Mo(CO) 3 (C 5 H 5 N) 3 (0.645 g, 1.55 mmol) in CH 2 Cl 2 (20 mL). The reaction mixture was stirred (3 h) while its color changed from yellow to pale orange; an IR spectrum ((CH 2 Cl 2 ) ν max (CO)/cm −1 1938 (s), 1835 (m) cm −1 ) indicated complete consumption of Mo (CO) 3 (C 5 H 5 N) 3 and Mo(CO) 2 (C 5 H 5 N) 2 (2-methallyl)Br formation.…”

“…1 Fluorinated tris(pyrazol-1-yl)borates represent a Tp ligand class that has gained prominence, particularly with Group XI metals, in stabilizing rare species such as π-acetylene complexes ([HB(3,5-(CF 3 ) 2 Pz) 3 ]M(C 2 H 2 ), [HB(3-(CF 3 )-5-(Ph)Pz) 3 ]M(C 2 H 2 ) (M = Cu, Ag)), 2 heterobimetallics with iron pentacarbonyl ligands ( e.g. , [HB(3,5-(CF 3 ) 2 Pz) 3 ]Ag–Fe(CO) 5 3 ), π-ethylene complexes ([HB(3-(CF 3 )-5-(CH 3 )Pz) 3 ]M′(C 2 H 4 ) (M′ = Cu, Ag, Au), 4 [HB(3,4,5-(CF 3 ) 3 Pz) 3 ]M(C 2 H 4 ) 5 ), complexes of 1-azidoadamantane ([HB(3,5-(CF 3 ) 2 Pz) 3 ]CuNNN(1-Ad), [HB(3,5-(CF 3 ) 2 Pz) 3 ]AgN(1-Ad)NN 6 ) and a silver( i ) complex of dimethyl diazomalonate ([HB(3,5-(CF 3 ) 2 Pz) 3 ]Ag[OC(OCH 3 )] 2 CN 2 7 ). Fluorinated tris(pyrazol-1-yl)borates also support catalytically active complexes including [HB(3,5-(CF 3 )-4-(Br)Pz) 3 ]Cu(NCCH 3 ), that catalyzes :CHCO 2 Et insertion into methane C–H bonds, 8 and {[HB(3,5-(CF 3 ) 2 Pz) 3 ]Zn(NCCH 3 ) 2 }ClO 4 that similarly catalyzes alkane C–H functionalization.…”

In situ pyrazolylborate ligand synthesis and coordination behaviours in aluminum oxo clusters

“…Therefore, the in situ ligands play an important role in inducing the aggregation of cluster compounds. Compared with the reported monomers and dimers bridged by classically prepared scorpionates, 14,[25][26][27] we successfully isolated a series of aluminum oxo clusters (AlOCs) via the in situ generation method. These ligands chelate two Al ions at the same time, acting as "edge" ligands and constructing dimeric, tetrahedral and belt-like hexanuclear clusters (Fig.…”