Chemistry of vinylidene complexes. XXIV. A new μ-vinylidene complex containing RePt core, and platinum-bound carbonyl ligand. Spectroscopic, structural and electrochemical study

The chelate complex [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) reacted, in the presence of CF3SO3Ag, with 1 equiv of C6H4(CºCH)2-p (4) to afford the mononuclear vinylidene compound [RuCl(C=CHC6H4-p-CºCH){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3) (3). From 1 and 0.5 equiv of 4, the binuclear bis(vinylidene) complex [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (6) was obtained. The related compound [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (7) was prepared from 1, 0.5 equiv of C6H4(CºCH)2-m (5), and silver triflate. The reaction of 2 or 3 with [RhCl(P-i-Pr3)2]2 (8) in the molar ratio of 2:1 yields, by addition of the 14-electron fragment [RhCl(P-i-Pr3)2] to the uncoordinated CC triple bond, the heterobinuclear complexes [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CºCH)RhCl(P-i-Pr3)2](CF3SO3) (9, 10) which slowly rearrange at room temperature to give the bis(vinylidene) isomers [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CH=C)RhCl(P-i-Pr3)2](CF3SO3) (11, 12).Key words: ruthenium, rhodium, vinylidene complexes, alkyne complexes, phosphine complexes.

Download Full-text

Chemistry of vinylidene complexes. XXV. Synthesis and reactions of binuclear µ-vinylidene RePt complexes containing phosphite ligands. Spectroscopic, structural and electrochemical study

Inorganica Chimica Acta ◽

10.1016/j.ica.2020.119463 ◽

2020 ◽

Vol 505 ◽

pp. 119463

Author(s):

Oleg S. Chudin ◽

Victor V. Verpekin ◽

Alexander A. Kondrasenko ◽

Galina V. Burmakina ◽

Dmitry A. Piryazev ◽

...

Keyword(s):

Electrochemical Study ◽

Vinylidene Complexes ◽

Phosphite Ligands

Download Full-text

Vinylidene, allenylidene, cyclic oxycarbene, and η2-alkyne complexes from reactions of (η5-C5Me5)OsCl(PPh3)2 with alkynes and alkynols

Canadian Journal of Chemistry ◽

10.1139/cjc-2020-0320 ◽

2021 ◽

Vol 99 (2) ◽

pp. 268-276

Author(s):

Sunny Kai San Tse ◽

Herman Ho-Yung Sung ◽

Ian Duncan Williams ◽

Guochen Jia

Keyword(s):

Molar Ratio ◽

Dimethyl Acetylenedicarboxylate ◽

Vinylidene Complexes ◽

Propargylic Alcohol ◽

Alkyne Complexes ◽

Vinylidene Complex ◽

Allenylidene Complex ◽

Internal Alkyne

Reactions of Cp*OsCl(PPh3)2 (Cp* = pentamethylcyclopentadienyl) with alkynes and alkynols are described. Treatment of Cp*OsCl(PPh3)2 with phenylacetylene and trimethylsilylacetylene gave the vinylidene complexes Cp*OsCl(=C=CHPh)(PPh3) and Cp*OsCl(=C=CH2)(PPh3), respectively. Treatment of Cp*OsCl(PPh3)2 with the internal alkyne dimethyl acetylenedicarboxylate produced the η2-alkyne complex Cp*OsCl(η2-MeO2C≡CCO2Me)(PPh3). Treatment of Cp*OsCl(PPh3)2 with the propargylic alcohol HC≡CC(OH)Ph2 gave the osmium allenylidene complex Cp*OsCl(=C = C=CPh2)(PPh3). The outcomes of the reactions of Cp*OsCl(PPh3)2 with ω-alkynols HC≡C(CH2)nOH are dependent on the length of the -(CH2)n- linker. The reaction with 3-butyn-1-ol produced the cyclic oxycarbene complex Cp*OsCl{=C(CH2)3O}(PPh3) exclusively. The reactions with 4-pentyn-1-ol produced a mixture of the hydroxyalkyl vinylidene complex Cp*OsCl{=C=CH(CH2)3OH}(PPh3) and the cyclic oxycarbene complex Cp*OsCl{=C(CH2)4O}(PPh3) in about 10:1 molar ratio. The reaction with 5-hexyn-1-ol gave exclusively the hydroxyalkyl vinylidene complex Cp*OsCl{=C=CH(CH2)4OH}(PPh3).

Download Full-text

Infrared study of transformation of a terminal carbonyl ligand into a bridging one in the MnPt and MnPd μ-vinylidene complexes

Journal of Molecular Structure ◽

10.1016/s0022-2860(96)09541-5 ◽

1997 ◽

Vol 408-409 ◽

pp. 329-332 ◽

Cited By ~ 6

Author(s):

Alfred A. Johansson ◽

Alla B. Antonova ◽

Nina I. Pavlenko ◽

Anatoly I. Rubaylo

Keyword(s):

Carbonyl Ligand ◽

Infrared Study ◽

Vinylidene Complexes

Download Full-text