TY - JOUR
T1 - Synthesis and crystal structure of iridium-1,4-benzoquinone complexes of tris(3,5-dimethylpyrazolyl)methane ligand
T2 - Decarbonylation, protonation, and substitution reactions
AU - Hernández-Juárez, Martín
AU - Salazar, Verónica
AU - García-Báez, Efrén V.
AU - Padilla-Martínez, Itzia I.
AU - Höpfl, Herbert
AU - Rosales-Hoz, Maria De Jesus
PY - 2012/8/13
Y1 - 2012/8/13
N2 - Complexes [κ 2-Tpm Me2Ir(2,3,5,6-η-2-R-1,4- benzoquinone)Cl] (R = H, 1a; Cl, 1b; Ph, 1c; tBu, 1d; Tpm Me2 = tris(3,5-dimethylpyrazolyl)methane) and [κ 3- Tpm Me2Ir(2,3,5,6-η-1,4-benzoquinone)][BF 4], 2a-BF 4, have been prepared from the dimeric complex [Ir(μ-Cl)(coe) 2] 2 and structurally characterized. Compounds 1a-d were then thermally transformed to the corresponding iridacyclohexa-2,5-dien-4-one complexes [κ 3-Tpm Me2Ir(1,5-η-CH=C(R)C(O)CH=CH-) (CO)][BF 4], 3-BF 4, and for 1a the reactivity toward CO, phosphines, and HBF 4-OEt 2 was examined. Compounds 1a, 1b, 2a-BF 4, 3a-BF 4, 3b-BF 4, carbonyl complex [κ 3-Tpm Me2Ir(2,3-η-1,4-benzoquinone)(CO)][Ir(CO) 2Cl 2], 4-[Ir(CO) 2Cl 2], phosphine complexes [(PR 3) 2Ir(2,3,5,6-η-1,4-benzoquinone)Cl] (PR 3 = PPh 3, PPhMe 2, PMe 3), 5-7, and [(μ-PPh 2CH 2CH 2PPh 2)Ir(2,3,5,6- η-1,4-benzoquinone)Cl] 2, 8, were characterized by X-ray diffraction analysis. Treatment of 1a with HBF 4 led, through the intermediacy of [κ 2-Tpm Me2Ir(2-6-η-semiquinone) Cl][BF 4], 9-BF 4, to the isolation of hydroquinone [κ 2-Tpm Me2Ir(1-6-η-1,4-hydroquinone)Cl][BF 4] 2, 10-(BF 4) 2, and treatment of 3-BF 4 with HSO 3CF 3 led to dicationic iridaphenol complexes [κ 3-Tpm Me2Ir(1,5-η-CH=C(R) -C(OH)=CH-CH=)(CO)][SO 3CF 3] 2 (R = H, tBu), 11-(O 3SCF 3) 2.
AB - Complexes [κ 2-Tpm Me2Ir(2,3,5,6-η-2-R-1,4- benzoquinone)Cl] (R = H, 1a; Cl, 1b; Ph, 1c; tBu, 1d; Tpm Me2 = tris(3,5-dimethylpyrazolyl)methane) and [κ 3- Tpm Me2Ir(2,3,5,6-η-1,4-benzoquinone)][BF 4], 2a-BF 4, have been prepared from the dimeric complex [Ir(μ-Cl)(coe) 2] 2 and structurally characterized. Compounds 1a-d were then thermally transformed to the corresponding iridacyclohexa-2,5-dien-4-one complexes [κ 3-Tpm Me2Ir(1,5-η-CH=C(R)C(O)CH=CH-) (CO)][BF 4], 3-BF 4, and for 1a the reactivity toward CO, phosphines, and HBF 4-OEt 2 was examined. Compounds 1a, 1b, 2a-BF 4, 3a-BF 4, 3b-BF 4, carbonyl complex [κ 3-Tpm Me2Ir(2,3-η-1,4-benzoquinone)(CO)][Ir(CO) 2Cl 2], 4-[Ir(CO) 2Cl 2], phosphine complexes [(PR 3) 2Ir(2,3,5,6-η-1,4-benzoquinone)Cl] (PR 3 = PPh 3, PPhMe 2, PMe 3), 5-7, and [(μ-PPh 2CH 2CH 2PPh 2)Ir(2,3,5,6- η-1,4-benzoquinone)Cl] 2, 8, were characterized by X-ray diffraction analysis. Treatment of 1a with HBF 4 led, through the intermediacy of [κ 2-Tpm Me2Ir(2-6-η-semiquinone) Cl][BF 4], 9-BF 4, to the isolation of hydroquinone [κ 2-Tpm Me2Ir(1-6-η-1,4-hydroquinone)Cl][BF 4] 2, 10-(BF 4) 2, and treatment of 3-BF 4 with HSO 3CF 3 led to dicationic iridaphenol complexes [κ 3-Tpm Me2Ir(1,5-η-CH=C(R) -C(OH)=CH-CH=)(CO)][SO 3CF 3] 2 (R = H, tBu), 11-(O 3SCF 3) 2.
UR - http://www.scopus.com/inward/record.url?scp=84864996775&partnerID=8YFLogxK
U2 - 10.1021/om300439c
DO - 10.1021/om300439c
M3 - Artículo
SN - 0276-7333
VL - 31
SP - 5438
EP - 5451
JO - Organometallics
JF - Organometallics
IS - 15
ER -