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• W2044779818 abstract "The reaction of dinuclear (Cp*RhCl2)2 (1) with the lithium butadienesulfinate salt Li[SO2CH═CHCH═CH2] (2-Li) in THF results in the formation of dimeric [Cp*Rh(Cl)2(5-η-SO2CH═CRCH═CHR)(Li)(THF)]2 (3) in 82% yield, while an excess of potassium butadienesulfinate, K[SO2CH═CHCH═CH2] (2-K), affords the mononuclear rhodium ion pair [Cp*RhCl(5-η-SO2CH═CHCH═CH2)(5-η-S(O2−K+)CH═CHCH═CH2)] (5-K) in 90% yield. Compound 5-K reacts with AgBF4 to give the neutral compound [Cp*Rh(1,2,5-η-SO2CH═CHCH═CH2)(5-η-SO2CH═CHCH═CH2)] (6) in 67% yield. The lability and low stability of 5-K as well as that of compound 3 were established by NMR and dynamic light scattering. A mixture of 5-K with 5 equiv of 2-K, under THF reflux, shows spectroscopic evidence of the trisubstituted [Cp*Rh(5-η-SO2CH═CHCH═CH2)2(5-η-S(O2−K+)CH═CHCH═CH2)] (7-K), which, in the presence of KCl, is in equilibrium with 5-K, thus preventing its isolation. By ESI-TOF-MS experiments of this mixture, the presence of aggregated species 5-K(2-K)n and 7-K(2-K)n (n = 1−3) has been detected. Organometallic−butadienesulfinate aggregates contrast with ruthenium complexes previously observed with butadienesulfonyl and butadienesulfinate ligands. Reactions of 3 and 5-K toward PR3 (R = Ph, Me) are not selective and afford mixtures of compounds [Cp*RhCl(5-η-SO2CH═CHCH═CH2)(PR3)] [R = Ph, (8); Me, (10)] and Cp*Rh(Cl)2PR3 [R = Ph, (9) Me, (11)]. The butadienesulfonyl ligands in 8 and 10 are in S- or W-conformation for the corresponding kinetic and thermodynamic products. Compound 3 favors the formation of 9 or 11, while 5-K favors that of isomer 8 or 10." @default.
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• W2044779818 date "2010-07-30" @default.
• W2044779818 modified "2023-09-26" @default.
• W2044779818 title "Chemistry of Butadienesulfinate Salts with (Cp*RhCl₂)₂ and the Reactivity of Their Derivatives with Tertiary Phosphines" @default.
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• W2044779818 doi "https://doi.org/10.1021/om901108y" @default.
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