Iridium hydride complexes with P,C,P pincer ligands based on ferrocene and ruthenocene

Russian Chemical Bulletin -     

Condensation of [2-(α-carbinol)norbornadiene]cyclopentadienylrhodium complexes with CH acid compounds

Conclusions The reaction of the 2-(-carbinol)norbornadiene complexes of rhodium with aliphatic nitro compounds and other CH acids was discovered, which leads under mild conditions to condensation products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 935–937, April, 1984.     

Reduction of (1,3-diformylindenyl)cyclopentadienylruthenium derivatives

The reduction of the (1,3-diformylindenyl)cyclopentadienylruthenium derivatives {η⁵-1,3-(CHO)₂C₉H₅}RuCp (Cp = C₅H₅), {η⁵-1,3-(CHO)₂C₉H₅}RuCp* (Cp* = C₅Me₅), and {η⁵-1,3-(CHO)₂C₉H₅}RuCpF (Cp^F = C₅Me₄CF₃) with NaBH₄ or LiAlH₄ under mild conditions affords the [1,3-bis(hydroxymethyl)indenyl]cyclopentadienylruthenium complexes {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp, {η⁵-1,3-(CH₂OH)₂C₉H₅}RuCp*, and {η⁵-1,3-(CH₂OH)₂C₉H₅}-RuCp^F, respectively, in good yields.     

Ruthenium complexes with ferrocene-based P,C,P pincer ligand

First ruthenium complexes with a ferrocene-based pincer ligand were synthesized. The cyclometallation of 1,3-bis[(di-tert-butylphosphino)methyl]ferrocene with RuCl₂(DMSO)₄ in 2-methoxyethanol afforded the RuCl(CO)[{2,5-(Bu^t ₂PCH₂)₂C₅H₂}Fe(C₅H₅)](RuCl(CO) ) complex (5). Complex 5 reversibly binds CO to form the RuCl(CO)₂ complex (6). The analogous reaction in the presence of NaBAr′₄ (Ar′ = 3,5-(CF₃)₂C₆H₃) produced the cationic complex {Ru(CO)₂ }BAr′₄ (7). The structures of complexes 5 and 7 were established by single-crystal X-ray diffraction. The X-ray diffraction study revealed an agostic interaction between one of the C-H bonds of the axial (exo-oriented with respect to the ferrocene iron atom) tert-butyl group and the Ru atom in complexes 5 and 7. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1695–1701, September, 2007.     

Activation of small molecules by a rhodium bis(phosphinite) pincer complex

Rhodium hydrido chloride pincer complex RhH(Cl)[2,6-(Bu^{pt b2}PO)^b2C^b6H^b3] was synthesized and used for the preparation of new complexes with labile two-electron ligands Rh(L)[2,6-(Bu^{pt b2}PO)^b2C^b6H^b3] (L = MeCN or S(CH^b2)^b4) and complexes with small molecules, such as CO, O^b2, H^b2, and N^b2.