TY - JOUR
T1 - Optically Active and C3-Symmetric Tris(pyrazolyl)hydroborate and Tris(pyrazolyl)phosphine Oxide Ligands
T2 - Synthesis and Structural Characterization
AU - LeCloux, Daniel D.
AU - Tokar, Christopher J.
AU - Osawa, Masahisa
AU - Houser, Robert P.
AU - Keyes, Michael C.
AU - Tolman, William B
PY - 1994/7/1
Y1 - 1994/7/1
N2 - We report multigram-scale syntheses of optically active thallium(I) tris(pyrazolyl)hydroborate {Tl[HB(pz*)3]} [pz* = 7(R)-isopropyl-4(R)-methyl-4,5,6,7-tetrahydroindazolyl (Menthpz) and 7(S)-tert-butyl-4(R)-methyl-4,5,6,7-tetrahydroindazolyl(Mementhpz)] and tris(pyrazolyl)- phosphine oxide [OP(pz*)]3 [pz* = (4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2-indazolyl (Camphpz), Menthpz, and Mementhpz] ligands of potential utility for stereoselective metal-mediated organic transformations, the assignment of their 1H and 13C NMR spectra using COSY and HETCOR methods, and representative X-ray crystal structures that define their absolute configurations and steric properties. X-ray structure data for OP(Camphpz)3: monoclinic, space group P21 (No. 4), at 24 °C, a = 6.841(4) Å, b = 18.657(8) Å, c = 12.633(4) Å, β = 103.62(4)°, V = 1567(2) Å3, Z = 2, R = 0.052, and Rw = 0.057 for 2564 reflections with I > 2σ(I) and 369 parameters. X-ray structure data for Tl[HB(Menthpz)3] (TlTpMenth): monoclinic, space group P212121 (No. 19), at 24 °C, a = 9.763(3) Å, b = 18.004(7) Å, c = 20.29(2)Å, V= 3566(5)Å3, Z = 4, R = 0.040, and Rw 0.038 for 4497 reflections with I > 2σ (I) and 370 parameters. X-ray structure data for Tl[HB(Mementhpz)3] (TlTpMementh): monoclinic, space group P212121 (No. 19), at 24 °C, a = 10.711(6) AÅ, b = 14.97(1) Å, c = 23.769(6) Å, V = 3811(7) Å3, Z = 4,R =0.050, and Rw = 0.053 for 3896 reflections with I > 2σ (I) and 397 parameters.
AB - We report multigram-scale syntheses of optically active thallium(I) tris(pyrazolyl)hydroborate {Tl[HB(pz*)3]} [pz* = 7(R)-isopropyl-4(R)-methyl-4,5,6,7-tetrahydroindazolyl (Menthpz) and 7(S)-tert-butyl-4(R)-methyl-4,5,6,7-tetrahydroindazolyl(Mementhpz)] and tris(pyrazolyl)- phosphine oxide [OP(pz*)]3 [pz* = (4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-4,7-methano-2-indazolyl (Camphpz), Menthpz, and Mementhpz] ligands of potential utility for stereoselective metal-mediated organic transformations, the assignment of their 1H and 13C NMR spectra using COSY and HETCOR methods, and representative X-ray crystal structures that define their absolute configurations and steric properties. X-ray structure data for OP(Camphpz)3: monoclinic, space group P21 (No. 4), at 24 °C, a = 6.841(4) Å, b = 18.657(8) Å, c = 12.633(4) Å, β = 103.62(4)°, V = 1567(2) Å3, Z = 2, R = 0.052, and Rw = 0.057 for 2564 reflections with I > 2σ(I) and 369 parameters. X-ray structure data for Tl[HB(Menthpz)3] (TlTpMenth): monoclinic, space group P212121 (No. 19), at 24 °C, a = 9.763(3) Å, b = 18.004(7) Å, c = 20.29(2)Å, V= 3566(5)Å3, Z = 4, R = 0.040, and Rw 0.038 for 4497 reflections with I > 2σ (I) and 370 parameters. X-ray structure data for Tl[HB(Mementhpz)3] (TlTpMementh): monoclinic, space group P212121 (No. 19), at 24 °C, a = 10.711(6) AÅ, b = 14.97(1) Å, c = 23.769(6) Å, V = 3811(7) Å3, Z = 4,R =0.050, and Rw = 0.053 for 3896 reflections with I > 2σ (I) and 397 parameters.
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U2 - 10.1021/om00019a048
DO - 10.1021/om00019a048
M3 - Article
AN - SCOPUS:0001376141
SN - 0276-7333
VL - 13
SP - 2855
EP - 2866
JO - Organometallics
JF - Organometallics
IS - 7
ER -