Iridium(I),Iridium(III),and Iridium(V) Complexes Containing the (2-Methoxyethyl)cyclopentadienyl Ligand

摘要

Treatment of [Ir(mu-Cl)(COE)_2]_2 (1) with LiCp~O gives Ir(eta~5-Cp~O)(COE)_2 (2; Cp~O = C_5H_4(CH_2)_2OCH_3,COE = cis-cyclooctene),which reacts with X_2 to afford the iridium(III) derivatives [Ir(eta~5-Cp~O)X(mu-X)]_2 (X = I (3),Cl (4)).Complexes 3 and 4 react with P~iPr_3 to yield the corresponding species Ir(eta~5-Cp~O)(P~i-Pr_3)X_2 (X = I (5),Cl (6)),which by addition of LiHBEt_3 give Ir(eta~5-Cp~O)(P~iPr_3)H_2 (7).The reactions of 5 and 6 with 2.0 equiv of AgBF_4 in acetonitrile lead to [Ir(eta~5-Cp~O)(P~iPr_3)(NCMe)_2][BF_4]_2 (8).Treatment of 3 with 2.0 equiv of HSiEt_3 per iridium affords the monohydride dimer [Ir(eta~5-Cp~O)I]_2(mu-H)(mu-I) (9).Complex 4 reacts with 4.0 equiv of HSiEt_3 per iridium to give the iridium(V) silyl trihydride derivative IrH_3(eta~5-Cp~O)(SiEt_3) (10),which in the presence of excess of HSiEt_3 is transformed into IrH_2(eta~5-Cp~O)-(SiEt_3)_2 (11).Treatment at -40 deg C of 4 with 2.0 equiv of HSiEt_3 per iridium leads to a mixture of the hydride dichloro triethylsilyl complex IrH(eta~5-Cp~O)Cl_2(SiEt_3) (12),the dihydride chloro triethylsilyl compound IrH_2(eta~5-Cp~O)Cl(SiEt_3) (14),and the monohydride dimer [Ir(eta~5-Cp~O)Cl]_2(mu-H)(mu-Cl) (16).Complex 16 has been also prepared by reaction of 4 with 1.0 equiv of HSiEt_3 per iridium.Complex 10 is easily deuterated in C_6D_6 at 80 deg C.The X-ray structures of 4,8,and 9 are also reported.