P,C,P-Pincer complexes of ruthenium based on ruthenocene and pentamethylruthenocene

The first ruthenocene- and pentamethylruthenocene-based ruthenium pincer complexes, RuCl(CO)[{2,5-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅H₅)] and RuCl(CO)[{2,5-(Bu^t ₂PCH₂)₂C₅H₂}Ru-(C₅Me₅)], were synthesized by cyclometallation of {1,3-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅H₅) and {1,3-(Bu^t ₂PCH₂)₂C₅H₂}Ru(C₅Me₅), respectively, with RuCl₂(DMSO)₄ in 2-methoxyethanol and characterized by ¹H and ³¹P{¹H} NMR spectroscopy, and X-ray diffraction.     

Photochromic transformations of cymantrenyl amides

Photochemical properties of N-acyl-substituted aminomethyl- and 1-aminoethylcymantrenes were studied for the first time. These compounds form photochromic systems in solutions due to the intermolecular exchange of ligands at the manganese atom.     

Iodine and cymantrenyl regioselective exchange in the η5-IC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex under cross-coupling conditions

The reaction of ⁵-IC₅H₄(CO)₂Fe-¹,⁵-C₅H₄Mn(CO)₃ with Me₃SiCCSiMe₃ (2 : 1) in the presence of Pd(MeCN)₂Cl₂ afforded the I(CO)₂Fe(C₅H₄—C₅H₄)Mn(CO)₃ complex generated through migrations of the I atom from the Cp ring to the Fe atom and of the C₅H₄Mn(CO)₃ group from the Fe atom to the Cp ring.     

Reaction of alkyne cluster Os3(μ-CO)(CO)9(μ3-η1:η1:η2-Me3SiC2Me) with HC≡CCOOMe. Molecular and crystal structures of Os3(CO)9{μ3-η1:η1:η2:η2-C(SiMe3)C(Me)C(COOMe)CH× and Os3(CO)8{μ3-η1:η1:η4:η1-C(SiMe3)C(Me)C(H)C(COOMe)CH× complexes

Reaction of the cluster Os₃(μ-CO)(CO)₉(μ₃-η¹:η¹:η²-Me₃SiC₂Me) with HC≡CCOOMe in benzene at 70 °C results in Os₃(CO)₉{μ₃-η¹:η¹:η²:η²-C(SiMe₃)C(Me)C(COOMe)CH× (5), Os₃(CO)₉{μ₃-η¹:η¹:η²:η²-C(SiMe₃)C(Me)C(H)C(COOMe)CH× (6), Os₃(CO)₉{μ-η¹:η¹:η⁴-C(SiMe₃)C(Me)C(H)C(COOMe)CH× (7), and Os₃(CO)_δ{μ₃-η¹:η¹:η⁴:η¹-C(SiMe₃)C(Me)C(H)C(COOMe)× complexes (8), containing an osmacyclopentadiene moiety. Complexes5–8 were characterized by¹H NMR and IR spectroscopy. The structure of clusters5 and8 was confirmed by X-ray analysis. Complex7 is formed from cluster5 as a result of a new intramolecular rearrangement and complex8 is obtained by decarbonylation of compound6. Complex8 adds PPh₃ to give Os₃(CO)_δ(PPh₃){μ-η¹:η¹:η⁴-C(SiMe₃)C(Me)C(H)C(COOMe)×.     

Reaction of Os3(μ-Cl)2(CO)10 with Ph2PCH2PPh2. The formation of a novel 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring

The reaction of Os₃(μ-Cl)₂(CO)₁₀ (1) with Ph₂PCH₂PPh₂ (dppm) in a toluene solution at 65°C results in novel osmium complexes [Os₃(μ-Cl)₂(CO)₉]₂(dppm) (2) and [Os₃(μ-Cl)₂(CO)₈]₂(dppm)₂ (3). Compounds 2 and 3 were characterized by¹H and³¹P NMR, and IR spectroscopy and their structures were established by X-ray analysis. In both compounds, dppm is a bridging ligand between the two cluster units. Molecule3 can be considered as an unusual 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1844–1851, September, 1998.     

Synthesis of the gold-dirhenium ferrocenylacetylide cluster. The crystal structure of Re2(μ-C≡CFc){Au(PPh3)}(CO)8

The thermal reaction of Re₂(CO)₈(NCMe)₂ with Au(CCFc)PPh₃ afforded the cluster Re₂(-CCFc){Au(PPh₃)}(CO)₈, which was characterized by X-ray diffraction analysis.     

Dicarbonyl chelates from 1-cymantrenylalkylamides with the dendrite structure: formation,photochromism, and kinetics of dark reaction with carbon monoxide

Photolysis of carboxamides of the dendrite structure with aminomethyland 1-aminoethylcymantrenes leads to the formation of six-membered dicarbonyl chelates with the Mn—O bond which are stable in solutions. The chelates in the reversed dark reaction with carbon monoxide give the starting tricarbonyl complexes. The formation of the chelates and their dark reaction are accompanied by the reversible change of color by the compounds. The rate determining step of the thermal reaction of chelates with CO is a chelate ring opening with the ligand substitution by the S_N1 mechanism. A possibility of solvent-free photoinduced ligand-exchange reaction in a number of cymantrene derivatives was demonstrated.     

Vibrational spectra and structure of “staircase” carbonyl π-complexes of transition metals

FTIR spectra have been studied for staircase cyclopentadienyl complexes comprising two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO)₂Fe-CpmMn(CO)₃ (1), Cp(CO)₂Fe-CpmFe(CO)₂CH₂Ph (2), Cp(CO)₂Fe-Cpm(CO)₂Fe-CpmMn(CO)₃ (3), Cp(CO)₂Mo-Cpm(CO)₂Fe-CpmMn(CO)₃ (4), Cp(CO)₃W- Cpm(CO)₂Fe-CpmMn(CO)₃ (5), Cp(CO)₂Fe-Cpm(CO)₂Fe-BmCr(CO)₃ (6), Cr(CO)₃Bm-CpmFe(CO)₂CH₂Ph (7), where Cp = ⁵-C₅H₅, Cpm = ¹⁵-C₅H₄, Bm = ¹⁶-C₆H₅, as well as mononuclear model complexes Cp(CO)₂Fe(CH)₂Ph (8), CpMn(CO)₃ (9), and (⁶-C⁶H⁶)Cr(CO)³ (10). The spectra were interpreted on the basis of the local symmetry of each metal carbonyl center. The positions of vCOs are determined by the mutual electronic effect of each center. CpmM(CO)_n groups are strong electron acceptors and cause an increase in vCOs of adjacent M(CO)_n groups. Cp(CO)_nM groups, being electron donors, cause a decrease in the frequencies of neighboring groups. In trinuclear complexes, the frequencies of the central Fe(CO)₂ group are not changed much due to the compensation of donor and acceptor influences of two neighboring substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1948–1951, November, 1994.This project was supported by the Russian Foundation for Basic Research (project code No. 93-03-18592).     

PCP pincer ligands based on metallocenes. Crystal structure of the rhodium complex cis-RhCl2(CO)[{2,5-(Pri2PCH2)2C5H2}Fe(C5H5)]

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