TY - JOUR
T1 - Synthesis and Characterization of Mixed-Ligand Cyclopentadienyl–Pyrazolylborate Complexes of Ruthenium
AU - McNaii, Amy M.
AU - Boyd, David C.
AU - Mann, Kent R
PY - 1986
Y1 - 1986
N2 - Neutral compounds of Ru(II) that contain a cyclopentadienyl and a pyrazolylborate ligand were synthesized from [CpRu(CH3CN)3]PF6 and [Cp*Ru(CH3CN)3]PF6 (Cp− = η5-cyclopentadienyl; Cp*- = η5-pentamethylcyclopentadienyl). [CpRu(HBpz3)], [CpRuHB(3, 5-Me2pz)3], [CpRuBpz4], and [Cp*Ru(HBpz3)] were characterized spectroscopically. An X-ray crystallographic study of [CpRu(HBpz3)] was completed. CpRu(HBpz3) crystallizes in the P21/m space group with Z = 2, V = 749.8 Å3, a = 9.0854 (4) Å, b = 10.074 (4) Å, c = 8.195 (2) Å, and (3 = 91.50 (3)°. Full-matrix least-squares refinement (112 variables, 2290 reflections) converged to give R and Rw values of 0.043 and 0.052, respectively. The structure consists of discrete (η5-Cp)Ru(HBpz3) units with Ru-C bonds of 2.153 (3) Å and Ru-N bonds of 2.128 (3) Å. Electrochemical measurements for the series of compounds were carried out for comparison with ferrocene and ruthenocene. The compounds exhibit a quasi-reversible, one-electron oxidation that falls in the range 0.145–0.463 V vs. Ag/AgCl. Oxidation of CpRuHB(3,5-Me2pz)3 with AgPF6 allowed the isolation of [CpRuHB(3,5-Me2pz)3]PF6. The thermal reactivity of these compounds allowed the synthesis of the new complexes [CpRuHB(3,5-Me2pz)3(CO)], [CpRuBpz4(CO)], and [Cp2Ru2(CO)2Bpz4]PF6 that exhibit bidentate coordination of pyrazolylborate ligands to ruthenium. While the CpRu pyrazolylborate complexes are formally similar to ruthenocene, the replacement of cyclopentadienyl with a pyrazolylborate ligand significantly alters the chemistry of these new compounds.
AB - Neutral compounds of Ru(II) that contain a cyclopentadienyl and a pyrazolylborate ligand were synthesized from [CpRu(CH3CN)3]PF6 and [Cp*Ru(CH3CN)3]PF6 (Cp− = η5-cyclopentadienyl; Cp*- = η5-pentamethylcyclopentadienyl). [CpRu(HBpz3)], [CpRuHB(3, 5-Me2pz)3], [CpRuBpz4], and [Cp*Ru(HBpz3)] were characterized spectroscopically. An X-ray crystallographic study of [CpRu(HBpz3)] was completed. CpRu(HBpz3) crystallizes in the P21/m space group with Z = 2, V = 749.8 Å3, a = 9.0854 (4) Å, b = 10.074 (4) Å, c = 8.195 (2) Å, and (3 = 91.50 (3)°. Full-matrix least-squares refinement (112 variables, 2290 reflections) converged to give R and Rw values of 0.043 and 0.052, respectively. The structure consists of discrete (η5-Cp)Ru(HBpz3) units with Ru-C bonds of 2.153 (3) Å and Ru-N bonds of 2.128 (3) Å. Electrochemical measurements for the series of compounds were carried out for comparison with ferrocene and ruthenocene. The compounds exhibit a quasi-reversible, one-electron oxidation that falls in the range 0.145–0.463 V vs. Ag/AgCl. Oxidation of CpRuHB(3,5-Me2pz)3 with AgPF6 allowed the isolation of [CpRuHB(3,5-Me2pz)3]PF6. The thermal reactivity of these compounds allowed the synthesis of the new complexes [CpRuHB(3,5-Me2pz)3(CO)], [CpRuBpz4(CO)], and [Cp2Ru2(CO)2Bpz4]PF6 that exhibit bidentate coordination of pyrazolylborate ligands to ruthenium. While the CpRu pyrazolylborate complexes are formally similar to ruthenocene, the replacement of cyclopentadienyl with a pyrazolylborate ligand significantly alters the chemistry of these new compounds.
UR - https://www.scopus.com/pages/publications/0000159299
UR - https://www.scopus.com/inward/citedby.url?scp=0000159299&partnerID=8YFLogxK
U2 - 10.1021/om00133a021
DO - 10.1021/om00133a021
M3 - Article
AN - SCOPUS:0000159299
SN - 0276-7333
VL - 5
SP - 303
EP - 310
JO - Organometallics
JF - Organometallics
IS - 2
ER -