Activation of SO₂ by [Zn(Cp∗)₂] and [(Cp∗)ZnI-ZnI(Cp∗)]

Interesting reactivity was observed in reactions of SO2 with [Zn(Cp*)2] and [(Cp*)ZnI–ZnI(Cp*)]. These reactions proceeded with insertion of SO2 into the Zn–C bonds. Spectacularly, the lability of the C–S bond in the O2SCp* ligands led to the thermal decomposition of [Zn(O2SCp*)2(tmeda)] to afford [Zn2(μ-SO3)(μ-S2O4)(tmeda)2]

Activation of SO 2 by [Zn(Cp*) 2 ] and [(Cp*)Zn I –Zn I (Cp*)]

International audienceInteresting reactivity was observed in reactions of SO2 with [Zn(Cp*)2] and [(Cp*)ZnI–ZnI(Cp*)]. These reactions proceeded with insertion of SO2 into the Zn–C bonds. Spectacularly, the lability of the C–S bond in the O2SCp* ligands led to the thermal decomposition of [Zn(O2SCp*)2(tmeda)] to afford [Zn2(μ-SO3)(μ-S2O4)(tmeda)2]

Chiral Rare Earth Borohydride Complexes Supported by Amidinate Ligands: Synthesis, Structure, and Catalytic Activity in the Ring-Opening Polymerization of rac-Lactide

International audienceThe monoamidinato bisborohydride rare earth complexes [Ln{(S)-PEBA}(BH4)2(THF)2] (Ln = Sc (1), La (2), Nd (3), Sm (4), Yb (5), Lu (6)) were isolated as crystalline materials upon treatment of potassium N,N′-bis((S)-1-phenylethyl)benzamidinate ((S)-KPEBA) with the homoleptic trisborohydrides [Sc(BH4)3(THF)2] and [Ln(BH4)3(THF)3] (Ln = La, Nd, Sm, Yb, Lu), respectively. Compounds 1-6 are unique examples of enantiopure borohydride complexes of the rare earth metals. Different ionic radii of the metal centers were selected to cover the whole range of these elements with respect to the extent of the coordination sphere. All new complexes were thoroughly characterized by 1H, 13C{1H}, 11B, and 15N NMR and IR spectroscopies, also including single-crystal X-ray diffraction structure determination of each compound. The scandium, lanthanum, samarium, and lutetium complexes 1, 2, 4, and 6 were found active in the ring-opening polymerization of rac-lactide under mild operating conditions, providing atactic α,ω-dihydroxytelechelic poly(lactic acid) (PLA; Mn,SEC up to 18 800 g*mol-1). Most of the polymerizations proceed with a certain degree of control that is directed by molar mass values and relatively narrow dispersities (1.10 < ĐM < 1.34), within a moderate monomer-to-initiator ratio

Chiral Rare Earth Borohydride Complexes Supported by Amidinate Ligands: Synthesis, Structure, and Catalytic Activity in the Ring-Opening Polymerization of <i>rac</i>-Lactide

The monoamidinato bisborohydride rare earth complexes [Ln­{(<i>S</i>)-PEBA}­(BH₄)₂(THF)₂] (Ln = Sc (<b>1</b>), La (<b>2</b>), Nd (<b>3</b>), Sm (<b>4</b>), Yb (<b>5</b>), Lu (<b>6</b>)) were isolated as crystalline materials upon treatment of potassium <i>N</i>,<i>N</i>′-bis­((<i>S</i>)-1-phenylethyl)­benzamidinate ((<i>S</i>)-KPEBA) with the homoleptic trisborohydrides [Sc­(BH₄)₃(THF)₂] and [Ln­(BH₄)₃(THF)₃] (Ln = La, Nd, Sm, Yb, Lu), respectively. Compounds <b>1</b>–<b>6</b> are unique examples of enantiopure borohydride complexes of the rare earth metals. Different ionic radii of the metal centers were selected to cover the whole range of these elements with respect to the extent of the coordination sphere. All new complexes were thoroughly characterized by ¹H, ¹³C­{¹H}, ¹¹B, and ¹⁵N NMR and IR spectroscopies, also including single-crystal X-ray diffraction structure determination of each compound. The scandium, lanthanum, samarium, and lutetium complexes <b>1</b>, <b>2</b>, <b>4</b>, and <b>6</b> were found active in the ring-opening polymerization of <i>rac</i>-lactide under mild operating conditions, providing atactic α,ω-dihydroxytelechelic poly­(lactic acid) (PLA; <i>M</i>_n,SEC up to 18 800 g·mol^–1). Most of the polymerizations proceed with a certain degree of control that is directed by molar mass values and relatively narrow dispersities (1.10 < <i>Đ</i>_M < 1.34), within a moderate monomer-to-initiator ratio