Hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes: synthesis, coordination chemistry, and ring-opening polymerization studies on cyclic esters.
The reaction of the hybrid scorpionate/cyclopentadienyl lithium salt [Li(bpzcp)(THF)] [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] with 1 equiv of RMgCl proceeds cleanly to give very high yields of the corresponding monoalkyl kappa(2)-NN-eta(5)-C(5)H(4) magnesium complexes [Mg(R)(kappa(2)-eta(5)-bpzcp)] (R = Me 1, Et 2, (n)Bu 3, (t)Bu 4, CH(2)SiMe(3) 5, CH(2)Ph 6). Hydrolysis of the hybrid lithium salt [Li(bpzcp)(THF)] with NH(4)Cl/H(2)O in ether cleanly affords the two previously described regioisomers: (bpzcpH) 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (a) and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (b). Subsequent reaction of the bpzcpH hybrid ligand with ZnR(2) quantitatively yields the monoalkyl kappa(2)-NN-eta(1)(pi)-C(5)H(4) zinc complexes [Zn(R){kappa(2)-eta(1)(pi)-bpzcp}] (R = Me 7, Et 8, (t)Bu 9, CH(2)SiMe(3) 10). Additionally, magnesium alkyls 1, 2, 4, and 5 can act as excellent cyclopentadienyl and alkyl transfers to the zinc metal center and yield zinc alkyls 7-10 in good yields. The single-crystal X-ray structures of the derivatives 4, 5, 7, and 10 confirm a 4-coordinative structure with the metal center in a distorted tetrahedral geometry. Interestingly, whereas alkyl magnesium derivatives 4 and 5 present a eta(5) coordination mode for the cyclopentadienyl fragment, zinc derivatives 7 and 10 feature a peripheral eta(1)(pi) arrangement in the solid state. Furthermore, the reaction of the hybrid lithium salt [Li(bpzcp)(THF)] with 1 equiv of ZnCl(2) in tetrahydrofuran (THF) affords very high yields of the chloride complex [ZnCl{kappa(2)-eta(1)(pi)-bpzcp}] (11). Compound 11 was used as a convenient starting material for the synthesis of the aromatic amide zinc compound [Zn(NH-4-MeC(6)H(4)){kappa(2)-eta(1)(pi)-bpzcp}] (12), by reaction with the corresponding aromatic primary amide lithium salt. Alternatively, aliphatic amide and alkoxide derivatives were only accessible by protonolysis of the bis(amide) complexes [M{N(SiMe(3))(2)}(2)] (M = Mg, Zn) and the mixed ligand complex [EtZnOAr)] with the hybrid ligand bpzcpH to afford [Zn(R){kappa(2)-eta(1)(pi)-bpzcp}] (R = N(SiMe(3))(2) 13, R = 2,4,6-Me(3)C(6)H(2)O 14) and [Mg{N(SiMe(3))(2)}(kappa(2)-eta(5)-bpzcp)] (15). Finally, alkyl and alkoxide-containing complexes 1-10 and 14 can act as highly effective single-component living initiators for the ring-opening polymerization of epsilon-caprolactone and lactides over a wide range of temperatures. Epsilon-caprolactone is polymerized within minutes to give high molecular weight polymers with medium-broad polydispersities (M(n) > 10(5), M(w)/M(n) = 1.45). Lactide afforded poly(lactide) materials with medium molecular weights and polydispersities as narrow as M(w)/M(n) = 1.02. Additionally, polymerization of L-lactide occurred without racemization in the propagation process and offered highly crystalline, isotactic poly(L-lactides) with very high melting temperatures (T(m) = 165 degrees C). Microstructural analysis of poly(rac-lactide) by (1)H NMR spectroscopy revealed that propagations occur without appreciable levels of stereoselectivity. Polymer end group analysis showed that the polymerization process is initiated by alkyl transfer to the monomer.
Departamento de Química Inorgánica y Analítica, Universidad Rey Juan Carlos, Móstoles-28933-Madrid, Spain.
Andrés
A
Garcés
Luis F
LF
Sánchez-Barba
Carlos
C
Alonso-Moreno
Mariano
M
Fajardo
Juan
J
Fernández-Baeza
Antonio
A
Otero
Agustín
A
Lara-Sánchez
Isabel
I
López-Solera
Ana María
AM
Rodríguez
D003500:Cyclization; D004952:Esters; D017616:Magnesium Compounds / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D017967:Zinc Compounds / Q000737:chemistry*
D004952:Esters; D017616:Magnesium Compounds; D011108:Polymers; D017967:Zinc Compounds