Polypyrazolylborates and Scorpionates

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

“…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).…”

“…Vigorous employment of tris(pyrazol-1-yl)borates continues within essentially every inorganic chemistry subfield, including coordination chemistry of transition metals and main group elements, materials chemistry, organometallic chemistry, ligand design and catalysis. 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 ).…”

“…Vigorous employment of tris( pyrazol-1-yl)borates continues within essentially every inorganic chemistry subfield, including coordination chemistry of transition metals and main group elements, materials chemistry, organometallic chemistry, ligand design and catalysis. 1 Fluorinated tris( pyrazol-1yl)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- ). 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.…”

“…CF = 250 Hz, 2 J CF = 9.4 Hz, m-C), 140.1 (dt,1 J CF = 250 Hz, 2 J CF = 15.4 Hz, p-F), 117.2 (dd, 2 J CF = 13.3 Hz, 3 J CF = 4.4 Hz, o-C), 50.0 (s, Me), i-C not observed. colorless solution was stirred for 150 min.…”

“…B NMR (128 MHz, C 6 D 6 ): δ 31.3 (s) 19. F{ 1 H} NMR (376 MHz, C 6 D 6 ): δ −136.6 (d,3 J FF = 20.3 Hz, m-F), −162.6 (t,3 J FF = 20.3 Hz, p-F) 1. H NMR (400 MHz, C 6 D 6 ): δ 6.71 (m, 2H, o-H), 2.37 (s, 12H, Me) 13.…”