Reactions of Trisodium Tetracarbonylmetalates(3-) of Manganese and Rhenium with Brϕnsted Acids and Other Electrophiles. Synthesis of H2M(CO)4- (M = Mn and Re), (CH3)2Re(CO)4-, the First Dialkyl Derivative of a Carbonylmetalate Trianion, and Related Anionic Species

Garry F.P. Warnock, Lyn Cammarano Moodie, John E. Ellis

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Abstract

Treatment of hexamethylphosphoramide (HMPA) solutions of the trisodium tetracarbonylmetalates(3-) of manganese and rhenium with excess liquid ammonia causes precipitation of very thermally stable materials (dec ≥300 °C) that are isolated in high yields (85-95%) and represent the first available pure samples of unsolvated Na3[M(CO)4]. Infrared and NMR spectral studies of the protonation of Na3[M(CO)4] in HMPA show initial formation of the new monohydrides, HM(CO)42-, which are then converted quantitatively to the dihydrides, H2M(CO)4-. The new manganese dihydride, which is isoelectronic with the first known carbonyl hydride, H2Fe(CO)4, and the previously established rhenium complex are isolated in high yields (75-80%) as the pure salts, [Ph4As] [cis-H2M(CO)4]. The monohydride dianions, HM(CO)42-, also react with Ph3SnCl to provide cis-H(Ph3Sn)M(CO)4-, which can be isolated as the Et4N+ salt for rhenium. The initial successful alkylation reactions of carbonylmetalates(3-) are also reported. Treatment of Na3[Re(CO)4] with methyl p-toluenesulfonate (MeOTs) in HMPA first provides MeRe(CO)42- (identified by IR), which can be protonated or further methylated to give cis-H(Me)Re(CO)4- or cis-(Me)2Re(CO)4-, both of which are isolated in good yields (70-80%) as Ph4E+ (E = P, As) salts. These represent the first isolated alkyl derivatives of metal carbonyl trianions. IR, 1H, and 13C NMR spectra also confirm that Na3[Re(CO)4] reacts with 1,4-butaneditosylate to provide solutions of the somewhat thermally unstable rhenacyclopentane CH2CH2C-H2CH2Re(CO)4-, the initial example of an anionic 18-electron metallacycloalkane. Infrared, 1H, and 13C NMR spectral data have been obtained for many of these compounds and are compared with those of analogous previously known iron and osmium species.

Original languageEnglish (US)
Pages (from-to)2131-2141
Number of pages11
JournalJournal of the American Chemical Society
Volume111
Issue number6
DOIs
StatePublished - Mar 1989

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