Coordination Chemistry of Ester-Functionalized Cp Ligands. The Atom-Economy Synthesis of Na[C<sub>5</sub>H<sub>4</sub>CO<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>OH] and Solid State Structures of [Rh{C<sub>5</sub>H<sub>4</sub>CO<sub>2</sub>(CH<sub>2</sub>)<sub>2</sub>OH}(CO)<sub>2</sub>] and [Rh<sub>2</sub>{μ-(C<sub>5</sub>H<sub>4</sub>CO<sub>2</sub>CH<sub>2</sub>)<sub>2</sub>}(NBD)<sub>2</sub>]
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The one-step synthesis of Na[C5H4CO2CH2CHCH2] (1) from NaCp and diallyl carbonate is presented together with a simple pathway for the synthesis of sodium hydroxyalkoxycarbonylcyclopentadienide, Na[C5H4CO2(CH2)2OH] (2). The latter new reagent is obtained in high yield by reacting NaCp with 1,3-dioxolan-2-one (ethylene carbonate). When (±)-4-methyl-1,3-dioxolan-2-one [(±)-1,2-propylene carbonate] is used, the ring-opening reaction leads to a mixture of the two regioisomers Na[C5H4CO2CH2CH(Me)OH] (3a) and Na[C5H4CO2CH(Me)CH2OH] (3b) in a 7:3 ratio. Reactions of 1 and 2 with FeCl2 and [Rh(L,L)Cl]2 [L,L = CO or L,L = 2,5-norbornadiene (NBD)] lead to the respective metal complexes [Fe(C5H4CO2CH2CHCH2)2] (4), [Fe{C5H4CO2(CH2)2OH}2] (5), [Rh(C5H4CO2CH2CHCH2)(CO)2] (6), [Rh{C5H4CO2(CH2)2OH}(CO)2] (7), and [Rh{C5H4CO2(CH2)2OH}(NBD)] (8). Additionally in the reaction of 2 with [Rh(L,L)Cl]2 the diester-bridged dinuclear adducts [Rh2{μ-(C5H4CO2CH2)2}(L,L)2] [L,L = CO (9); L,L = NBD (10)] are isolated. The reaction of 2 with MBr(CO)5 (M = Mn, Re) leads to [M{C5H4CO2(CH2)2OH}(CO)3] [M = Mn (11); M = Re (12)] together with a complex mixture of unidentified metal carbonyls. The X-ray molecular structures of 7 and 10 are reported.
