Fluoborates of Mn(Re) ?-cyclopentadienyldicarbonylnitrosyl cations and some of their transformations

Reduction of coordinated carbon monoxide. Synthesis of neutral metal formyl and hydroxymethyl derivatives of the (cyclopentadienyl)dicarbonyl(nitrosyl)rhenium(1+) cation

“…Methanolysis of Metallo Ester Dimer (C5H5XCOXNO)-ReCOiCFhRefCOXNOXCsHs). Nesmeyanov reported that reduction of cation 1 by sodium borohydride in benzene-water produces an orange, air-sensitive solid, mp 69-71 °C dec. 10 The structure of the solid was assigned to be the hydroxymethyl complex (C5H5)Re(CO)(NO)(CH2OH) (3) on the basis of elemental analysis (C, , N, Re) and IR spectra [3300-3200 (s), 3120 (s), 2935 (s), 1980 (s), 1660 (s), 1420 (m), 1350-1260 (w), 1070 (m), 1010 (m), and 825 cm-1 (m)]. An NMR spectrum was not reported.…”

“…Treatment of 9 with 0.1 equiv of trifluoroacetic acid in THF-water, concentration, and extraction with toluene gave an orange solid. Spectral data, however, indicated that it was not hydroxymethyl complex 3 but the ether dimer [(C5H5)(CO)(NO)ReCH2]20 (10). 19 The desired hydroxymethyl complex was finally obtained when the acid-catalyzed hydrolysis of the methoxymethyl complex 9 was quenched with 0.15 equiv of triethylamine prior to workup.…”

Neutral metal formyl complexes: generation, reactivity, and models for Fischer-Tropsch catalyst intermediates

“…Received May 8,1978 Neutral Metal Formyl Complexes: Generation, Reactivity, and Models for Fischer-Tropsch Catalyst Intermediates Sir:…”

“…The reaction of [(C5H5)Re(CO)(PPh3)NO]+BF4-(3)10 with 1.0 equiv of Li(C2Hs)3BH (or K(sec-C4Hg)3BH) at 22 °C in THF yields the much more stable formyl (C5H5)-Re(PPh3)(NO)(CHO) (4) (Scheme I).11 Solvent removal, silica gel chromatography (under N2 using hexanes-THF), and THF-hexane recrystallization afford honey-colored, analytically pure crystals11 in 59% yield (dec pt (gradual) ~91 °C). THF (-23) 100 13.45 (s) rapid dec (10) [Re(CO)5PPh3]+BF4- (6) CH2C12 (-23) 90 13.98 (s)rf rapid dec (20) [Mn(CO)4(PPh3)2]+PF6- (7) CH2C12 (-22) 71 13.23 (t/ 4) rapid dec (0) [Ir(CO)3(PPh3)2]+PF6- (8) CH2C12 (-60) 80 12.85 (t, 17) rapid dec (-30) [(C5H5)Mo(CO)3PPh3]+PF6- (9) CH2C12 (-41) 41 14.70 (d, 4) rapid dec (-41)…”

“…Relative to (CH4)4Si at the temperature of generation; chemical shifts are temperature dependent. Li^LDaBH is reacted with metal carbonyl cations [5][6][7][8][9] (Table I). 10 By analogy to 2 and 4, and in some cases subsequent transformations, these products are formulated as neutral formyl complexes.…”