Organometallic complexes in synthesis. Part IV. Abstraction of hydride from some tricarbonylcyclohexa-1,3-dieneiron complexes and reactions of the complexed cations with some nucleophiles

Synthesis and reactivity of [(η6-[32](1,3)Cyclophane)Mn(CO)3][BF4]

“…have reported that reaction of (6-hexamethylbenzene)-(g 4 -[2 2 ](1,4)cyclophane)ruthenium with hydrochloric acid gives (6-hexamethyl-benzene)(g 5 -3H- [2 2 ] (1,4)cyclophane)ruthenium(II) hydrogen dichloride, compound 3 apparently is the first example of preparing a [(g 5 -6H-[3 2 ](1,3)cyclophane)Mn(CO) 3 ] complex [15,16]. There are a few instances of hydride addition yielding a mixture of exo and endo products [17]. Thus, a brief study of reaction with sodium cyanoborodeuteride was undertaken to confirm whether the hydride donor adds to 2 exo or endo to the manganese.…”

Synthesis, Molecular Structure, Fluxional Behavior, and Tricarbonyliron Transfer Reactions of (η4-1-Azabuta-1,3-diene)tricarbonyliron Complexes

“…[12] [13] (η 4 -1-Azabuta-1,3-diene)tricarbonyliron complexes were first described by Otsuka [14] and Lewis [15] and have been applied to the synthesis of dicarbonyl(η 4 -styrHowever, the problematic step of this reaction sequence ene)iron carbene complexes, [16] substituted pyrroles, [17] and is the preparation of the transfer reagent 4. The original to the preparation of labile Schiff bases in the form of their procedure described by Lewis involved complexation of metal complexes.…”

“…[8] The reaction conditions at temperatures below 0°C. Moreover, using GrevelsЈ reagent 6 also non-conjugated 1,4-dienes can (η 4 -benzylideneacetone)tricarbonyliron (4) was found to represent an especially efficient transfer reagent. Brookhart be complexed with concomitant migration of the double bond, e.g.…”

“…Complexation of cyclohexa-1,3-diene (1a) and cyclohexa-1,4-diene (1b) with Fe(CO) 5 or Fe 2 (CO) 9 found many useful applications in synthetic organic chemistry and have been shown to represent excellent starting materials for the stereoselective synthesis of natural products. [1] The parent complex, tricarbonyl(η 4 -cyclohexa-1,3-diene)iron (2), was prepared first in 1958 by Pauson via complexation of cyclohexa-1,3-diene (1a) with pentacarbonyliron under thermal reaction conditions (yield: 21%). [2] The yield of this complexation was later improved by photolytic reaction of cyclohexa-1,4-diene (1b) with pentacarbonyliron in benzene (yield: 56%), [3] by reaction of cyclohexa-1,4-diene (1b) with pentacarbonyliron in di-n-butyl ether at reflux (yield: 46%), [4] by reaction of cyclohexa-resulting tricarbonyl(η 5 -cyclohexadienylium)iron tetra-1,3-diene (1a) with nonacarbonyldiiron in tetrahydrofuran fluoroborate (3) can be utilized for regio-and stereoselecat reflux (yield: 43%), [5] and by photolytic reaction of cyclo-tive bond formation with a broad range of nucleophiles.…”

“…[1] The parent complex, tricarbonyl(η 4 -cyclohexa-1,3-diene)iron (2), was prepared first in 1958 by Pauson via complexation of cyclohexa-1,3-diene (1a) with pentacarbonyliron under thermal reaction conditions (yield: 21%). [2] The yield of this complexation was later improved by photolytic reaction of cyclohexa-1,4-diene (1b) with pentacarbonyliron in benzene (yield: 56%), [3] by reaction of cyclohexa-1,4-diene (1b) with pentacarbonyliron in di-n-butyl ether at reflux (yield: 46%), [4] by reaction of cyclohexa-resulting tricarbonyl(η 5 -cyclohexadienylium)iron tetra-1,3-diene (1a) with nonacarbonyldiiron in tetrahydrofuran fluoroborate (3) can be utilized for regio-and stereoselecat reflux (yield: 43%), [5] and by photolytic reaction of cyclo-tive bond formation with a broad range of nucleophiles. [1] hexa-1,3-diene (1a) with pentacarbonyliron in hexane Projected synthetic applications of the complex salt 3 re-(yield: 77%) [5] (Scheme 1).…”