American Chemical Society
ja039365k_si_001.cif (31.74 kB)

Hydration of Nitrosylruthenium Bis(alkynyl) Complexes with Hydrotris(pyrazolyl)borate:  Insertion/Hydration and Double Hydration Products

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posted on 2004-03-31, 00:00 authored by Yasuhiro Arikawa, Yoshimasa Nishimura, Kenta Ikeda, Masayoshi Onishi
Hydration of nitrosylruthenium bis(alkynyl) complex TpRu(C⋮CPh)2(NO) (1) (Tp = BH(pyrazol-1-yl)3) was carried out in the presence of HBF4·Et2O in distilled MeOH and afforded the metallacycle TpRu{CHC(Ph)C(O)CH(Ph)}(NO) (2) (39%) and the bis(ketonyl) TpRu(CH2C(O)Ph)2(NO) (3) (37%). While double hydration of 1 gave 3, 2 was produced through a combination of insertion and hydration processes. On the other hand, a similar reaction performed in THF instead of MeOH afforded 2 (52%), the acyl-ketonyl complex TpRu(C(O)CH2Ph)(CH2C(O)Ph)(NO) (4) (8.9%), and trace amounts of 3 and TpRu(C⋮CPh)(CH2C(O)Ph)(NO) (5). Moreover, the 1/HBF4·Et2O/H2O reaction system in distilled MeOH at 0 °C gave rise to 5 exclusively (79%). Treatment of THF solution of isolated 5 with water in the presence of protic acid furnished 3 and 4, revealing that 5 is the intermediate in their formation.