Synthesis and characterization of copper(I) complexes with a fairly bulky tris(pyrazolyl)hydroborate ligand. Probing the flexibility of the metal-containing pocket formed by the ligand

Four copper(I) tris(pyrazolyl)hydroborate complexes are reported with the fairly bulky tris[3-(p-tert-butylphenyl)-5-methylpyrazol-1-yl]hydroborate ligand (Tp(tBu-Ph,Me)). Tp(tBu-Ph,Me)Cu(CH3CN) (1) was synthesized from CuCl and Tp(tBU-Ph,Me)Li(CH3CN). The acetonitrile ligand in 1 was easily replaced by CO, PPh3, and (PBu3)-Bu-t, forming Tp(tBu-Ph,Me)Cu(CO) (2), Tp(tBu-Ph,Me)Cu(PPh3) (3), and Tp(tBu-Ph,Me)Cu((PBu3)-Bu-t) (4), respectively. Complexes 1-4 have been crystallographically characterized. 1.4CH(3)CN, 173 K: C52H67BCuN11, triclinic, P (1) over bar, a = 13.4201(10) Angstrom, b = 15.132(2) Angstrom, c = 15.2125(13) Angstrom, alpha = 60.743(6)degrees, beta = 73.211(4)degrees, gamma = 74.839(5)degrees, Z = 2, R1 = 6.81% (wR2 = 18.91%). 2, 296 K: C43H52BCuN6O, monoclinic, C2/c, a = 25.592(4) Angstrom, b = 12.434(2) Angstrom, c = 28.044(3) Angstrom, beta = 104.073(9)degrees, Z = 8, R1 = 7.47% (wR2 = 22.08%). 3.CH2Cl2, 173 K: C61H69BCl2CuN6P, triclinic, P (1) over bar, a = 12.5080(13) Angstrom, b = 15.159(3) Angstrom, c = 17.151(2) Angstrom, alpha = 64.271(10)degrees, beta = 79.073(7)degrees, gamma = 86.572(8)degrees, Z = 2, R1 = 5.13% (wR2 = 13.28%). 4.0.5 hexane, 298 K: C57H86BCuN6P, triclinic, P (1) over bar, a = 13.337(2) Angstrom, b = 13.435(2) Angstrom, c = 17.386(2) Angstrom, alpha = 88.371(7)degrees, beta = 71.886(8)degrees, gamma = 80.223(9)degrees, Z = 2, R1 = 6.96% (wR2 = 18.62%). The Tp(tBu-Ph,Me) ligands in 1, 2, and 3 bind in a tridentate fashion; the CH3CN and CO ligands fit comfortably within the pocket formed by the tert-butylphenyl substituents and the PPh3 ligand interleaves between the pyrazole arms. The flexibility of the pocket was probed by calculating the area of the triangle created by connecting the midpoints of the 3-phenyl groups; this parameter increases by 15% for 3 (the largest) over 1 (the smallest). Thus, the pocket exhibits some flexibility, found to be due to both steric and electronic factors. Complex 4 features a bidentate Tp(tBu-Ph,Me) ligand as the (PBu3)-Bu-t apparently exceeds the pocket's flexibility.