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Novel heteroscorpionate rare-earth-metal complexes (Y, La, and Lu) have been developed for the coupling reaction of CO2 and cyclohexene oxide under mild conditions. The reaction of an alcohol heter...

Despite the great interest in zinc catalysis for hydroelementation reactions, the use of zinc complexes as catalysts for the hydroalkoxylation of alkynyl alcohols has not been reported to date. Scorpionate zinc complexes have been successfully designed as precatalysts for the hydroalkoxylation reaction of alkynyl alcohols under mild reaction conditions. Zinc amide complex

Nonisocyanate polyurethane materials with pending alcohol groups in the polymeric chain were synthesized by polyaddition reaction of bis(cyclic carbonates) onto diamines. For the platform molecule, 1,4-butanediol bis(glycidyl ether carbonate) (BGBC, 1) was used. The polyaddition reaction of 1 onto a wide range of diamines with different electronic and physical properties was explored. All PHUs were obtained quantitatively after 16 h at 80 °C temperature in MeCN as solvent. The low nucleophilicity of L-lysine has proven unable to ring-open the cyclic carbonate and, thus, no reaction occurred. The addition of DBU or TBD as the catalyst was tested and allows the obtention of the desired PHU. However, the presence of strong bases also led to the formation of polyurea fragments in the new PHU. The different poly(hydroxyurethane) materials were characterized using a wide range of spectroscopic techniques such as NMR, IR, MALDI-ToF, and using GPC studies. The thermal properties of the NIPUs were investigated by DSC and TGA analyses. Moreover, reactions employing different monomer ratios were performed, obtaining novel hydroxycarbamate compounds. Finally, sequential and one-pot experiments were also carried out to synthesize the PHUs polymers in one-step reaction.

Two new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily p...

The coupling reaction of carbon dioxide and terminal, internal, and highly substituted epoxides derived from renewable resources such as furfural, limonene, carvone, carvyl acetate, terpinen-4-ol, ...

Helical aluminium complexes [Al2X4(μ-nbptam)] (X = Me 1, Et 2), [Al2X4(μ-fbpam)] (R = Me 3, Et 4), [Al3X7(μ-nbptam)] (X = Me 5, Et 6) and [Al3X7(μ-fbpam)] (X = Me 7, Et 8) have been prepared by treatment of scorpionate ligand precursors with two or three equivalents of the corresponding trialkylaluminium derivative. The structures of these complexes have been determined by spectroscopic methods and the X-ray crystal structure of complex 1 has also been established. These complexes have been studied as catalysts for the chemical fixation of carbon dioxide into cyclic carbonates displaying good catalytic activity. When cyclohexene oxide was used as a substrate, polyether-polycarbonate was obtained in a ratio which is highly dependent on the cocatalyst and the catalyst to cocatalyst ratio used.

Preprint A series of new chiral zwitterionic NNO-scorpionate mononuclear zinc alkyls [Zn(R)(κ3-NNO)]Br was developed in very high yields via suitable quaternization in the scorpionate ligand. These zwitterionic complexes performed as bifunctional catalysts and exhibited improved catalytic activity for the fixation of CO2 into cyclic carbonates compared to the neutral analog mononuclear [Zn(R)(κ3-NNO)] and binuclear [Zn(R)(κ2-NNμ-O)Zn(R)2] compounds. The catalyst system showed a broad substrate scope and functional group tolerance under mild and solvent-free conditions.

The direct reaction of the highly sterically demanding acetamidinate-based NNN′-scorpionate protioligand Hphbptamd [Hphbptamd = N,N′-di-p-tolylbis(3,5-di-tertbutylpyrazole-1-yl)acetamidine] with one equiv. of ZnMe2 proceeds in high yield to the mononuclear alkyl zinc complex [ZnMe(κ3-phbptamd)] (1). Alternatively, the treatment of the corresponding lithium precursor [Li(phbptamd)(THF)] with ZnCl2 yielded the halide complex [ZnCl(κ3-phbptamd)] (2). The X-ray crystal structure of 1 confirmed unambiguously a mononuclear entity in these complexes, with the zinc centre arranged with a pseudotetrahedral environment and the scorpionate ligand in a κ3-coordination mode. Interestingly, the inexpensive, low-toxic and easily prepared complexes 1 and 2 resulted in highly efficient catalysts for the ring-opening polymerisation of lactides, a sustainable bio-resourced process industrially demanded. Thus, complex 1 behaved as a single-component robust initiator for the living and immortal ROP of rac-lactide under very mild conditions after a few hours, reaching a TOF value up to 5520 h−1 under bulk conditions. Preliminary kinetic studies revealed apparent zero-order dependence on monomer concentration in the absence of a cocatalyst. The PLA materials produced exhibited narrow dispersity values, good agreement between the experimental Mn values and monomer/benzyl alcohol ratios, as well as enhanced levels of heteroselectivity, reaching Ps values up to 0.74.

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

New mono- and dinuclear chiral alkoxide/thioalkoxide NNO-scorpinate zinc complexes were easily synthesized in very high yields, and characterized by spectroscopic methods. X-ray diffraction analysis unambiguously confirmed the different nuclearity of the new complexes as well as the variety of coordination modes of the scorpionate ligands. Scorpionate zinc complexes 2, 4 and 6 were assessed as catalysts for polycarbonate production from epoxide and carbon dioxide with no need for a co-catalyst or activator under mild conditions. Interestingly, at 70 &deg, C, 10 bar of CO2 pressure and 1 mol % of loading, the dinuclear thioaryloxide [Zn(bpzaepe)2{Zn(SAr)2}] (4) behaves as an efficient and selective one-component initiator for the synthesis of poly(cyclohexene carbonate) via ring-opening copolymerization of cyclohexene oxide (CHO) and CO2, affording polycarbonate materials with narrow dispersity values.

Two new derivatives of the bis(3,5-dimethylpyrazol-1-yl)methane modified by introduction of organosilyl groups on the central carbon atom, one of which bearing a chiral fragment, have been easily prepared. We verified the potential utility of these compounds through the reaction with [Zr(NMe

Novel bimetallic zinc acetate complexes supported by heteroscorpionate ligands have been developed for the ring-opening copolymerization of cyclohexene oxide and CO2 and the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2. Heteroscorpionate ligands precursors L1-L3 were reacted with two equivalents of zinc acetate to afford the dinuclear zinc complexes [{Zn(κ3-bpzappe)}(μ-O2CCH3)3-{Zn(HO2CCH3)}] (1), [{Zn(κ3-bpzbdmape)}(μ-O2CCH3)3-{Zn(HO2CCH3)}] (2), and [{Zn(κ3-bpzbdeape)}(μ-O2CCH3)3{Zn(HO2CCH3)}] (3) in excellent yields. The molecular structure of these compounds was determined spectroscopically and confirmed by X-ray diffraction analysis. Zinc acetate complexes 1-3 were screened as catalysts for the copolymerization of cyclohexene oxide and CO2 to produce poly(cyclohexene)carbonate, and complex 3 was found to be the most active catalyst for this process in the absence of a cocatalyst. Furthermore, the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2 was studied using the combination of complex 3 and 4-dimethylaminopyridine as catalyst system yielding the corresponding polyester-polycarbonate materials.

Preprint A new family of bimetallic helical aluminum complexes can be obtained via warming up the preliminary dinuclear adduct complexes, or alternatively, by direct heating of the protioligands with 2 equiv of AlR3. X-ray diffraction analysis corroborated both high coordination versatility in the ligands and the existence of helical chirality in the complexes. DFT calculations confirmed the preferential arrangement of the ancillary scorpionates in the bimetallic complexes and rationalized a proposed reaction mechanism. Bimetallic complexes were investigated as catalysts in combination with halides for the cycloaddition reaction of CO2 with a wide range of epoxides for cyclic carbonate formation. These studies led to the development of a sustainable, inexpensive, efficient and selective bicomponent system with very broad substrate scope, including internal and challenging bio-based trisubstituted terpene derived substrates, reaching high conversions for translimonene oxide at mild conditions (79% conv., 70 ºC, 10 bar CO2, 1 mol%, 66 h).

The optimization of an organoaluminum catalytic system for the copolymerization of epoxides and anhydrides is presented. For this purpose, the influence of different variables in the process, such as catalysts, cocatalyst, solvent, or substrates, has been analyzed. Kinetic studies, a proposal for the catalytic mechanism, and full characterization of the copolymers obtained are also discussed. Finally, a new copolymer, poly(limonene succinate), obtained by the optimized catalytic system is reported.

Bifunctional aluminum complexes supported by novel zwitterionic NNO-donor scorpionate ligands were found to be efficient bifunctional catalysts for cyclic carbonate synthesis from terminal and internal epoxides in good yields and with broad substrate scope. Neutral scorpionate ligands (1–2) were designed and used as precursors to obtain two novel zwitterionic NNO-heteroscorpionate ligands (3–4). Reaction of 3 or 4 with [AlX3] (X = Me, Et) in a 1:1 or 1:2 molar ratio afforded the mononuclear and dinuclear cationic aluminum complexes [AlX2{κ2-mbpzbdmape}]I2 (X = Me (5), Et (6)), [AlX2{κ2-mbpzbdeape}]I2 (X = Me (7), Et (8)), [{AlX2(κ2-mbpzbdmape)}(μ-O){AlX3}]I2 (X = Me (9), Et (10)), and [{AlX2(κ2-mbpzbdeape)}(μ-O){AlX3}]I2 (X = Me (11), Et (12)) with elimination of the corresponding alkane. These complexes were investigated as catalysts for cyclic carbonate formation from epoxides and carbon dioxide in the absence of a co-catalyst. Complex 7 was found to be the most active catalyst for cyclic carbonate form...

A series of alkyl aluminium complexes based on heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters and ring-opening copolymerisation of epoxides and anhydrides. Treatment of AlX3 (X = Me, Et) with ligands bpzbeH [bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide], bpzteH [bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide], and (R,R)-bpzmmH [(R,R)-bpzmm = (1R)-1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] for 2 hours at 0 °C afforded the mononuclear dialkyl aluminium complexes [AlMe2{κ2-bpzbe}] (1), [AlEt2{κ2-bpzbe}] (2), [AlMe2{κ2-(R,R)-bpzmm}] (3) and [AlEt2{κ2-(R,R)-bpzmm}] (4), and the dinuclear dialkyl complexes [AlMe2{κ2-bpzte}]2 (5) and [AlEt2{κ2-bpzte}]2 (6). The molecular structures of the new complexes were determined by spectroscopic methods and confirmed by X-ray crystallography. The alkyl-containing aluminium complexes can act as highly efficient single-component initiators for the ring-opening polymerisation of ε-caprolactone and l-lactide and for the ring-opening copolymerisation of cyclohexene oxide and phthalic anhydride to give a range of biodegradable polyesters.

Highly efficient neutral and ionic imidazole-based organocatalysts have been developed for the synthesis of cyclic carbonates from epoxides and carbon dioxide. The ionic derivatives performed as bifunctional catalysts and exhibited improved activity for the fixation of CO2 compared to the neutral compounds. Mechanistic studies revealed that the hydroxyl group promoted the activation of the epoxide facilitating the epoxide ring-opening by nucleophilic attack of the iodide.

A new lanthanum heteroscorpionate complex has shown exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide. This catalyst system also promotes the reaction of bio-based epoxides to give an important class of bis(cyclic carbonates) that can be further used for the production of bio-derived non-isocyanate polyurethanes. The catalytic process requires low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates.

The reaction of the low sterically hindered heteroscorpionate lithium acetamidinates [Li(κ3-NNN)(thf)] {NNN = pbpamd (1) [pbpamd = N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], tbpamd (2) [tbpamd = N-ethyl-N′-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], ttbpamd (3) [ttbpamd = N,N′-di-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate], phbpamd (4) [phbpamd = N,N′-di-p-tolylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] and the highly sterically demanding [Li(κ3-phbptamd)(thf)] (5) [phbptamd = N,N′-di-p-tolylbis(3,5-di-tert-butylpyrazol-1-yl)acetamidinate] with the commercially available Grignard reagent tBuMgCl in an equimolecular ratio yielded the magnesium tert-butyl heteroscorpionates [Mg(tBu)(κ3-NNN)] [NNN = pbpamd (6), tbpamd (7), ttbpamd (8), and phbptamd (9)]. In addition, subsequent reaction of monoalkyls 6–8 with two additional equivalents of tBuMgCl gave rise to two different classes of chiral tetraalkyls, which contain apical methine C–H activated heteroscorpionates that...

A series of new chiral zwitterionic NNO-scorpionate mononuclear zinc alkyls [Zn(R)(κ3-NNO)]Br was developed in very high yields via suitable quaternization in the scorpionate ligand. These zwitterionic complexes performed as bifunctional catalysts and exhibited improved catalytic activity for the fixation of CO2 into cyclic carbonates compared to the neutral analog mononuclear [Zn(R)(κ3-NNO)] and binuclear [Zn(R)(κ2-NNμ-O)Zn(R)2] compounds. The catalyst system showed a broad substrate scope and functional group tolerance under mild and solvent-free conditions.

New bifunctional aluminum complexes have been prepared with the aim of studying the effect of a counterion on the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2). Neutral liga...

Preprint A novel nucleophilic addition of an organolithium to a ketenimine to prepare an enantiopure NNN-heteroscorpionate ligand is described. We verified its potential utility as a valuable scaffold for chirality induction through the preparation of enantiopure zinc complexes, which behave as highly efficient initiators to produce highly-enriched isotactic poly(lactide)s (Pi up to 0.88).

The chiral, enantiopure bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the alcohol compounds bpzbeH (bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide), bpzteH (bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide), and (R,R)-bpzmmH ((R,R)-bpzmm = (1R)-1-{(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide) have been used to obtain new NNO-heteroscorpionate yttrium and lutetium complexes. The reactions of bpzbeH, bpzteH (racemic mixtures), and (R,R)-bpzmmH (enantiopure compound) with [M{N(SiHMe2)2}3(thf)2] (M = Y, Lu) in a 1:1 molar ratio in toluene afforded the mononuclear bis(silylamide) complexes [M{N(SiHMe2)2}2(κ3-NNO)(thf)] (M = Y, Lu; 1–6), respectively. When the reaction was carried out with a 2:1 molar ratio (ligand to metal precursor) or with excess ligand, homoleptic complexes of the type [Y(κ3-NNO)2(κ-O-NN)] (κ3-NNO = κ-O-NN = bpzbe (7), bpzte (8)) were obtained. Compounds 1 and 3 were used as convenient st...

The reaction of chiral alcohol–scorpionate compounds bpzbeH [bpzbeH = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butanol] or bpzteH [bpzteH = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethanol] with [ZnR2] (R = Me, Et, CH2SiMe3) in a 1:2 molar ratio afforded the dinuclear chiral zinc alkyls [Zn(R)(κ2-NNµ-O)Zn(R)2] (1–4) [κ2-NNµ-O = bpzbe, R = Me (1), Et (2), CH2SiMe3 (3); bpzte, R = Et (4)]. Subsequent alcoholysis or thioalcoholysis reaction with ArEH (1 equiv.; E = O, S; Ar = 2,6-C6H3Me2) yielded the chiral dinuclear mixed alkyl–alryl oxides/thioaryl oxides [(ZnR)2(κN:κN-µ-O)(µ-EAr)] (5–12) [κN:κN-µ-O = bpzbe, E = O, R = Me (5), Et (6), CH2SiMe3 (7); bpzte, E = O, R = Et (8); bpzbe, E = S, R = Me (9), Et (10), CH2SiMe3 (11); bpzte, E = S, R = Et (12)]. The alcoholysis reaction of the previously reported monoalkyls [Zn(Me)(κ3-NNO)] or [Zn(R)(κ-NNµ-O)]2 with ArOH (1 equiv., Ar = 2,6-C6H3Me2) afforded the chiral aryl oxides [Zn(OAr)(κ2-NNµ-O)]2 (13–14) [κ2-NNµ-O = bpzbe (13); bpzte (14)]. The X-ray crystal structures of 3, 5, 6, and 14 confirmed a dinuclear structure in all cases with the alkoxide of the heteroscorpionates in a µ-bridging mode between the ZnII centers. Variable-temperature NMR spectroscopic studies were carried out to study their dynamic behavior in solution. Complexes 1–9 and 12 can act as single-component initiators for the ROP of e-CL and l-/rac-LA, and afforded materials with low molecular weights and narrow monomodal molecular weight distributions. MALDI-TOF mass spectra confirmed that for 5–8 the initiation occurred through nucleophilic attack by the alkoxide group, rather than the alkyl group, on the lactide monomer. Furthermore, inspection of the kinetic parameters showed propagations with a pseudo-first-order dependence on monomer and catalyst concentrations. Microstructural analysis of poly(rac-lactide) revealed that the mixed alkyl/aryl oxide-substituted initiators exert a moderate level of heteroselectivity (Ps = 0.66).

A series of new acetate and trifluroacetate bimetallic zinc complexes containing heteroscorpionate ligands have been prepared in very high yields. The structures of the complexes were determined by spectroscopic methods, and the single-crystal X-ray structure of complex 6 confirmed a κ3-NNO coordination mode of the scorpionate ligand in a dinuclear molecular arrangement. Bimetallic zinc complexes 6–11 were investigated as catalysts for the synthesis of polycarbonates from epoxides and carbon dioxide in the absence of a cocatalyst. Under the optimal reaction conditions, complex 10 acts as an efficient single-component initiator for the ring-opening copolymerisation of cyclohexene oxide and carbon dioxide, yielding polycarbonate materials with narrow polydispersities.

Preprint The reaction of the highly sterically demanding NNN′-heteroscorpionate protioligands pbptamd-H, tbptamd-H, and phbptamd-H (a) and the low sterically hindered analogs pbpamd-H, tbpamd-H, and phbpamd-H (b), with 1 equiv of AlR3 (R = Me, Et) proceed in high yields to give two families of complexes: the mononuclear dialkyl aluminum bidentate-acetamidinates [AlR2(κ2-N′N′)] (κ2-N′N′ = pbptamd, R = Me 1, Et 2; tbptamd, R = Me 3, Et 4; phbptamd, R = Me 5, Et 6) and the monodentate-acetamidinates [AlR2(κ2-NN′)] (κ2-NN′ = tbpamd, R = Me 7; phbpamd, R = Me 8, Et 9). In complexes 7–9, the presence of two possible CH–NH tautomers as low extended π-N–C–N′(sp2)–Al and high extended π-HN–C2–N′(sp2)–Al complexes, respectively, could be identified. Moreover, the reaction of aluminum dimethyls 7 and 8 with ZnMe2 afforded the isolation of the more stable scorpionate zinc monoalkyls [Zn(Me)(κ3-NNN′)] (NNN′ = tbpamd 10 and phbpamd 11), through a very unusual ligand exchange process, involving a zinc-to-aluminum transmetalation of an alkyl group. The X-ray crystal structures of 1, 3, 7, and 8, as well as that of 11, confirmed unambiguously the different κ2-arrangements proposed for bi- or monodentate acetamidinate dialkyls 1–6 and 7–9, respectively, the presence of NH tautomer in 7 and 8, and a κ3-NNN′ coordination in monoalkyl 11. Density functional theory calculations were used to explore the three different favored κ2-arrangements found in acetamidinate aluminum dialkyls 1–9, the relative stability of both CH–NH tautomers, and the ligand transfer reaction leading to the formation of κ3-NNN′ zinc monoalkyls 10 and 11. Interestingly, dialkyls 1, 5, 7, and 8 can act as highly efficient single-component living initiators for the ring-opening polymerization of ε-caprolactone and rac-lactide in mild conditions after hours. These initiators efficiently mediated the immortal polymerization in the presence of excess of benzyl alcohol (up to 20 equiv), as evidenced by the narrow dispersity values and the good agreement between the experimental Mn values and monomer/benzyl alcohol ratios. In addition, the most sterically hindered initiator, 5, exhibits enhanced levels of heteroselectivity on the produced PLAs, reaching Ps values up to 0.70.

A series of alkyl organoaluminium complexes based on bulky heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters. Thus, the treatment of AlX3 (X = Me, Et) with bulky acetamide or thioacetamide heteroscorpionate ligands nbptamH (1) [nbptamH = N-naphthyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide], fbpamH (2) [fbpamH = N-fluorenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamide], ptbptamH (3) [ptbptamH = N-phenyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)thioacetamide], ntbptamH (4) [ntbptamH = N-naphthyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)thioacetamide], ptbpamH (5) [ptbpamH = N-phenyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)acetamide] and (S)-mtbpamH (6) [(S)-mtbpamH = (S)-(−)-N-α-methylbenzyl-2,2-bis(3,5-di-tert-butylpyrazol-1-yl)acetamide] for 1 hour at 0 °C afforded the dialkyl aluminium complexes [AlX2{κ(2)-nbptam}] (X = Me 7, Et 8), [AlX2{κ(2)-fbpam}] (X = Me 9, Et 10), [AlX2{κ(2)-ptbptam}] (X = Me 11, Et 12), [AlX2{κ(2)-ntbptam}] (X = Me 13, Et 14), [AlX2{κ2(-)ptbpam}] (X = Me 15, Et 16) and [AlX2{κ(2)-(S)-mtbpam}] (X = Me 17, Et 18). The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structure of 14 was also established. The alkyl-containing aluminium complexes 7–18 can act as efficient single-component initiators for the ring-opening polymerisation of ε-caprolactone and rac-lactide. The polymerisations are living, as evidenced by the narrow polydispersities of the isolated polymers and the linear nature of the number average molecular weight versus conversion plot. Finally, a comparative study of ring-opening polymerisation for new bulky heteroscorpionate aluminium initiators and the less congested aluminium analogues is reported.

The synthesis, characterization and fluxional behaviour of novel heteroscorpionate rare-earth (including the group 3 metals, scandium and yttrium) complexes are reported. The reaction of acetamide and thioacetamide heteroscorpionate protio-ligands pbptamH, tbptamH, pbpamH and (S)-mbpamH with 1 equivalent of tris(silylamide) precursors [M{N(SiHMe2)2}3(thf)n] (n = 1, M = Sc; n = 2, M = Y, Lu) proceeded to give good yields of neutral heteroscorpionate disilylamide complexes [M{N(SiHMe2)2}2(κ3-pbptam)(thf)n] (M = Sc, n = 0, 1; M = Y, n = 1, 2; M = Lu, n = 1, 3), [M{N(SiHMe2)2}2(κ3-tbptam)(thf)n] (M = Sc, n = 0, 4; M = Y, n = 1, 5; M = Lu, n = 1, 6), [M{N(SiHMe2)2}2(κ3-pbpam)(thf)n] (M = Sc, n = 0, 7; M = Y, n = 1, 8; M = Lu, n = 1, 9) and [M{N(SiHMe2)2}2{κ3-(S)-mbpam}(thf)n] (M = Sc, n = 0, 10; M = Y, n = 1, 11; M = Lu, n = 1, 12). Scandium complexes were isolated as THF-free compounds with a pseudo five-coordinate environment, while yttrium and lutetium complexes were isolated with an octahedral geometry due to the coordination of a THF molecule. The fluxionality of complexes 1–12 in solution was investigated by VT NMR spectroscopy. The structures of these compounds were determined by spectroscopic methods and the X-ray crystal structure of 1 was also established. Complexes 1–12 are efficient catalysts for the intramolecular hydroamination of aminoalkenes, with TOF values up to 198 h−1 obtained at 70 °C for 2,2-diphenyl-pent-4-enylamine (13) using complex 11 as a catalyst. Enantioselectivities of up to 99% ee were achieved with the cyclization of aminoalkene 13 using the single enantiopure complex 12. The hydroamination reactions showed a zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration.

A series of enantiopure alkoxide and thioalkoxide zirconium derivatives [Zr(ER)3(κ3-R,R-fbpza)] (1–6) (E = O, R = CHMe21, CHMeEt 2, CH2SiMe33, 2,6-C6H3Me24, 4-tBuPh 5; E = S, R = 4-tBuPh 6) has been prepared for use as thermally stable and robust initiators in the ROP of rac-lactide. The compounds were prepared by alcoholysis or thioalcoholysis of the tris(amide) precursor [Zr(NMe2)3(κ3-R,R-fbpza)] [R,R-fbpzaH = N-p-fluorophenyl-(1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethylamine] with ROH and ArEH (E = O, S) in a 1 : 3 molar ratio. The structures of the different compounds were determined by spectroscopic methods and, in addition, the X-ray crystal structure of 6 was also established. Interestingly, the tris(amide) precursor and complexes 2, 5, and 6 act as single-site living initiators for the well-controlled ring-opening polymerization of rac-lactide both in solution and in the melt. These processes produce polymers with medium molecular weights in good agreement with theoretical values and with narrow dispersity ranges. The activity of all initiators increased markedly with temperature and, more importantly, complex 2 exhibits the highest activity reported to date for a group 4-based initiator in the ROP of rac-LA under the industrially preferred melt and solvent-free conditions. Surprisingly, complex 2 is still highly active in the melt when using an unpurified monomer and it shows an unprecedented tolerance to water and impurities (49% conv., 15 min, 130 °C). Microstructural analysis of the poly(rac-lactide)s revealed a moderate heteroactivity in solution, with a Ps value of up to 0.70.

Preprint The preparation of new chiral bis(pyrazol-1-yl)methane-based N,N,O-donor scorpionate ligands in the form of the alcohol compounds bpzampeH (1) {2,2-bis(3,5-dimethylpyrazol-1-yl)-1-[4-(dimethylamino)phenyl]ethanol}, bpzaepeH (2) {2,2-bis(3,5-dimethylpyrazol-1-yl)-1-[4-(diethylamino)phenyl]ethanol}, and bpzimeH (3) {2,2-bis(3,5-dimethylpyrazol-1-yl)-1-[1-methyl-1H-imidazol-2-yl]ethanol} has been carried out by the 1,2-addition reactions of a series of aldehydes. These new chiral heteroscorpionate ligands reacted with [ZnR2] (R = Me, Et, CH2SiMe3) in a 1 : 1 molar ratio in toluene to give the mononuclear monoalkyl zinc complexes [Zn(R)(κ3-NNO)] (4–12). When these reactions were carried out in a 1 : 2 molar ratio the binuclear trisalkyls [Zn(R)(κ2-NNμ-O)Zn(R)2] (13–18) were obtained. The structures of these complexes were elucidated by 1H and 13C{1H} NMR spectroscopy and the X-ray crystal structures of 4 and 5 were also established. Interestingly, alkyl-containing zinc complexes 4–13, 15 and 17 act as efficient single-component initiators for the ring-opening polymerization of rac-lactide at 20 °C to afford PLA materials with low molecular weights in a few hours. The dinuclear trisalkyls showed higher activity in comparison with the mononuclear zinc counterparts, suggesting a cooperative effect of the two remote metals. The narrow dispersity ranges (Mw/Mn = 1.05) of the isolated polymers in conjunction with the linear nature of the number average molecular weight versus conversion plot provided evidence for living behavior. Inspection of the kinetic parameters showed that the propagations have the usual pseudo-first-order dependence on rac-lactide and catalyst concentration. End-group analysis and MALDI-TOF mass spectrometry confirmed that the initiation occurs through nucleophilic attack of the alkyl on the lactide monomer. Microstructural analysis of poly(rac-lactide)s revealed that the most sterically hindered ligand on the alkoxide fragment exerts a moderate influence on the degree of stereoselectivity, with heteroenriched-PLAs (Ps = 0.68) produced at room temperature.

The reaction of the lithium dithioacetate derivative [Li(bdmpzdta)(THF)] [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] with 1 equiv. of C3H5MgCl proceeds in high yield to give the first alkaline-earth-metal complex bearing an asymmetrical gem-dithiolato moiety, namely, [Mg(κ3-NNS-μ-S-bppbte)]3 (1) [bppbte = 1,1-bis(3,5-dimethyl-1H-pyrazol-1-yl)pent-4-ene-2,2-bis(thiolate)]. This is achieved through an unprecedented insertion reaction of the allyl group into the C=S bond. In contrast, the reaction with the Grignard reagents MeMgCl or EtMgCl leads to the formation of the six-coordinate sandwich species [Mg(κ3-bdmpzdta)2] (2), as a result of a rapid ligand redistribution. The molecular structures of 1 and 2 in the solid state have been unambiguously established by single-crystal X-ray diffraction studies, which reveal a trinuclear entity with a twisted six-membered core for 1, in which all magnesium centers are arranged in a distorted trigonal bipyramidal geometry, whereas in 2 the magnesium center has an octahedral coordination environment with two heteroscorpionato ligands, which bind in a κ3-NNS fashion with a relative trans disposition.

The previously described reaction of the low sterically hindered heteroscorpionate lithium acetamidinates [Li(κ(3)-pbpamd)(THF)] and [Li(κ(3)-tbpamd)(THF)] with a series of commercially available Grignard reagents RMgCl in an equimolecular ratio yielded the magnesium monoalkyls [Mg(R)(κ(3)-NNN)] (NNN = pbpamd, R = CH2SiMe3, Et (1), Bn (2); NNN = tbpamd, R = CH2SiMe3, Et (3), Bn (4)). However, subsequent reaction of these monoalkyls [Mg(R)(κ(3)-NNN)] with two additional equivalents of the same RMgCl in tetrahydrofuran gave rise to dinuclear dialkyls of the type [RMg(κ(3)-N,N,N;κ(2)-C,N)MgR(thf)] (κ(3)-N,N,N;κ(2)-C,N = pbpamd(-), R = CH2SiMe3 (5), Et (6); κ(3)-N,N,N;κ(2)-C,N = tbpamd(-), R = CH2SiMe3 (7), Et (8)). Furthermore, when the reaction was carried out in a mixture of tetrahydrofuran/dioxane with the same stoichiometry, a new family of tetranuclear tetraalkyl magnesium complexes [{RMg(κ(3)-N,N,N;κ(2)-C,N)MgR}2{μ-O,O-(C4H8)}] (κ(3)-N,N,N;κ(2)-C,N = pbpamd(-), R = CH2SiMe3 (9), Et (10), Bn (11); κ(3)-N,N,N;κ(2)-C,N = tbpamd(-), R = CH2SiMe3 (12), Et (13), Bn (14)) was obtained. In both families, an apical methine C-H activation process on the heteroscorpionate takes place. The single-crystal X-ray structures of 4, 8, 9, and 12 confirm the nuclearity of each family, with 4-coordinative arrangements for all magnesium atoms. More importantly, the presence in the di- and tetranuclear complexes of unprecedented apical carbanions with a direct σ-C(sp(3))-Mg covalent bond, and as a result, the existence of stereogenic magnesium centers, have been unambiguously confirmed. Interestingly, the dinuclear dialkyls 5 and 7, as well as the tetranuclear tetraalkyls 9, 10, and 12, can act as highly efficient single-component living initiators for the ring-opening polymerization of ε-caprolactone and lactides. Lactide (LA) polymerizations afforded polylactide (PLA) materials with medium molecular weights in only a few minutes even at 20 °C for L-LA and in a few hours at 50 °C for rac-LA propagations. More importantly, microstructural analysis of the poly(rac-lactide) materials revealed that the tetranuclear tetra-alkyl 12 exerts enhanced levels of heteroselectivity on the PLAs under mild conditions, with Ps values up to 0.78.

Macromolecular engineering of cyclic polycaprolactones has been carried out by a ring-expansion procedure catalyzed by a series of alkyl-organoaluminum initiators. The single-site nature of the initiators allows a very well-controlled macrolactonization process to give moderate to high molecular weight cyclic polymers with narrow polydispersities. Cyclic architectures are supported by a combination of techniques such as viscosity measurements, NMR, and MALDI-TOF MS analysis.

The work described here represents the first example of an enantiopure hybrid scorpionate/cyclopentadiene ligand. The ligand was obtained in a one-pot synthetic procedure by an efficient and highly diastereoselective nucleophilic addition of an organolithium reagent to an electrophilically activated olefin in a new fulvene with a chiral substrate to control the stereochemistry of a newly created asymmetric center. We verified the potential utility of this ligand as a valuable scaffold that is able to induce chirality in organometallic/coordination chemistry. This was achieved through the preparation of a new enantiomerically pure zinc complex in which the ligand behaves in a tridentate manner with a κ2NN-η1(π)-Cp coordination mode. This alkylzinc complex constitutes the first example of an organozinc derivative which behaves as an efficient initiator for the ROP of rac-LA in the production of isotactic-enriched poly(lactides) with Pi = 0.77.

Preprint Reaction of chiral alcohol-scorpionate compoundbpzteH [bpzteH = 2,2-bis(3,5-dimethylpyrazol- 1-yl)-1-para-tolylethanol] with [ZnR2] (R = Me, CH2SiMe3) in a 1:2 molar ratio afforded the dinuclear chiral alkyl zinc complexes [Zn(R)(k2-NN μ-O)Zn(R)2] (1–2) [k2-NN μ-O= bpzte, R = Me 1, CH2SiMe32]. Using these trialkyl complexes in an alcoholysis reaction with ArOH (1 equiv; Ar = 2,6-C6H3Me2) yielded the chiral dinuclear zinc complexes [(ZnR)2(kN:kN- μ-O)( μ-EAr)] (3– 4) [kN:kN- μ-O= bpzte, R = Me 3, CH2SiMe34]. The structures of the different compounds were determined by spectroscopic methods and, in addition, the X-ray crystal structures of 1 and 3 confirmed a dinuclear structure in all complexes, with the alkoxide of the heteroscorpionate ligands in a μ-bridging mode between the two Zn(II) centers. Trisalkyl and alkyl-aryloxide-containing zinc complexes 1–4 can act as single-component initiators for the ring-opening homopolymerization of e-caprolactone and L-/rac-lactide, affording materials with low molecular weights and narrow monomodal molecular weight distributions under mild conditions in only a few hours. Microstructural analysis of poly(rac-lactide) revealed that the alkyl-aryloxide 3 exerts a moderate level of heteroselectivity (Ps= 0.68). More interestingly, this initiators 3 and 4 also allowed the well-controlled random copolymerization of ε-CL and LLA as indicated by both the values of the reactivity ratios of the two comonomers (rCL = 1.15 and 0.92, and rLA = 1.37 and 1.05, for 3 and 4, respectively), and the average lengths of the caproyl and lactidyl sequences (LCL ~ 2.0; LLA ~ 2.5, for both initiators). The copolymers also showed to possess monomer contents in close agreement with their composition in the initial monomer feed. Inspection by differential scanning calorimetry on the thermal properties such as Tg of various copolymers produced by 3 revealed a strong dependence on monomer content, as these values vary linearly with the molar percentage of L-lactide unit in the copolymer over a temperature range of -30 to 42 ºC.

The chiral and the enantiopure bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the alcohol compounds (bpzbeH) [bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide], (bpzteH) [bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide], and (R,R)-bpzmmH {(R,R)-bpzmm = (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide} have been utilized to obtain new NNO-scorpionate zinc alkyl complexes. The reaction of bpzbeH, bpzteH (racemic mixture), or (R,R)-bpzmmH (enantiopure) with [ZnMe2] in a 1:1 molar ratio in toluene afforded the mononuclear and monoalkyl zinc complexes [Zn(Me)(κ3-NNO)] (1–3), respectively. However, when the same reaction was carried out with [ZnEt2], [ZntBu2], or [Zn(CH2SiMe3)2], new dinuclear complexes of the type [Zn(R)(κ-NNμ-O)]2 (κ-NNμ-O = bpzbe, R = Et 4, tBu 5, CH2SiMe36; bpzte, R = Et 7, tBu 8, CH2SiMe39; (R,R)-bpzmm, R = Et 10, tBu 11, CH2SiMe312) were obtained. The single-crystal X-ray structure...

The reactions of the hybrid scorpionate/cyclopentadiene compounds, as a mixture of regioisomers—1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene and 2-[2,2-bis(3,5-dimeth...

The reaction of the sterically hindered heteroscorpionate lithium acetamidinate [Li(κ3-pbptamd)(THF)] (pbptamd = N,N′-diisopropylbis(3,5-di-tert-butylpyrazol-1-yl)acetamidinate) and [Li(κ3-tbptamd)...

The synthesis, structures, and ring-opening polymerization (ROP) activity of heteroscorpionate aluminum alkyl and aryloxide complexes are reported. The reactions of the acetamide and thioacetamide heteroscorpionate protio ligands pbptamH (pbptamH = N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)thioacetamide), pbpamH (pbpamH = N-phenyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamide), sbpamH (sbpamH = N-sec-butyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamide), and (S)-mbpamH ((S)-mbpamH = (S)-(−)-N-α-methylbenzyl-2,2-bis(3,5-dimethylpyrazol-1-yl)acetamide) with 1 equiv of AlR3 (R = Me, Et, iBu) proceed in very high yields to give the neutral heteroscorpionate dialkyl aluminum complexes [AlR2{κ2-pbptam}] (R = Me (1), Et (2)), [AlR2{κ2-pbptam}] (R = Me (3), Et (4), iBu (5)), [AlR2{κ2-pbptam}] (R = Me (6), Et (7), iBu (8)), and [AlR2{κ2-(S)-mbpam}] (R = Me (9), Et (10)). In the solid state, complexes 1−10 adopt a tetrahedral structure with the heteroscorpionate ligands arranged in a κ2 coordination mode; in the case of t...

The preparation of new chiral bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the lithium derivatives [Li(bpzb)(THF)] [1; bpzb = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide] and [Li(bpzte)(THF)] [2; bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide] or the alcohol ligands (bpzbH) (3) and (bpzteH) (4) has been carried out by 1,2-addition reactions with trimethylacetaldehyde or p-tolualdehyde. The separation of a racemic mixture of the alcohol ligand 3 has been achieved and gave an enantiopure NNO alcohol-scorpionate ligand in three synthetic steps: (i) 1,2-addition of the appropriate lithium derivative to trimethylacetaldehyde, (ii) esterification and separation of diastereoisomers 5, (iii) saponification. Subsequently, the enantiopure scorpionate ligand (R,R)-bpzmmH {6; R,R-bpzmmH = (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol} was obtained with an excellent diastereomeric excess (99% de) in a one-pot process utilizing the aldehyde (1R)-(-)-myrtenal as a chiral substrate to control the stereochemistry of the newly created asymmetric center. These new chiral heteroscorpionate ligands reacted with [MX(4)] (M = Ti, Zr; X = NMe(2), O(i)Pr, OEt, O(t)Bu) in a 1:1 molar ratio in toluene to give, after the appropriate workup, the complexes [MX(3)(kappa(3)-NNO)] (7-18). The reaction of Me(3)SiCl with [Ti(NMe(2))(3)(bpzb)] (7) or [Ti(NMe(2))(3)(R,R-bpzmm)] (11) in different molar ratios gave the halide-amide-containing complexes [TiCl(NMe(2))(2)(kappa(3)-NNO)] (19 and 20) and [TiCl(2)(NMe(2))(kappa(3)-NNO)] (21 and 22) and the halide complex [TiCl(3)(kappa(3)-NNO)] (23 and 24). The latter complexes can also be obtained by reaction of the lithium compound 1 with TiCl(4)(THF)(2) and deprotonation of the alcohol group of 6 with NaH, followed by reaction with TiCl(4)(THF)(2) in a 1:1 molar ratio, respectively. Isolation of only one of the three possible diastereoisomers of the complexes 19 and 22 revealed that chiral induction from the ligand to the titanium center took place. The structures of these complexes were elucidated by (1)H and (13)C{(1)H} NMR spectroscopy, and the X-ray crystal structures of 3-7, 12, and 24 were also established. Finally, we evaluated the influence that the chiral center of the new heteroscorpionate complexes has on the enantioselectivity of the asymmetric epoxidation of allylic alcohols.

The reactivity of hybrid scorpionate/cyclopentadienyl ligand-containing trichloride zirconium complexes [ZrCl 3 (bpzcp)] ( 1 ) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and [ZrCl 3 (bpztcp)] ( 2 ) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1- tert -butylethylcyclopentadienyl] toward several lithium alkoxides has been carried out. Thus, alkoxide-containing complexes [ZrCl 2 (OR)(bpzcp)] (R = Me, 3 ; Et, 4 ; i Pr, 5 ; ( R )-2-Bu, 6 ), [ZrCl 2 (OR)(bpztcp)] (R = Me, 7 ; Et, 8 ; i Pr, 9 ; ( R )-2-Bu, 10 ) and [Zr(OR) 3 (bpztcp)] (R = Et, 11 ; i Pr, 12 ) were prepared by deprotonation of the appropriate alcohol group with Bu n Li followed by reaction with 1 or 2 . In addition, the imido-complex [Ti(N t Bu)Cl(bpztcp)(py)] ( 13 ) were also prepared. The structures of these complexes have been proposed on basis of spectroscopic and DFT methods.

This review concerns the recent studies carried out by our research group and others aimed at the design of heteroscorpionate ligands based on bis(pyrazol-1-yl)methane-containing stereogenic centres. The capability of these systems to stabilize chiral complexes from early to late transition metals, through their behaviour as multidentate hybrid ligands, is also described.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Reaction of hybrid scorpionate/cyclopentadienyl ligands in the form of the lithium derivatives [Li(bpzcp)(THF)] [bpzcp=2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl], [Li(bpztcp)(THF)] [bpztcp=2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl], and the in situ-generated "Li(bpzpcp)" [bpzpcp=2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethylcyclopentadienyl] with MCl3(THF)3 afforded the group 3 halide compounds [MCl2(bpzcp)(THF)] (M=Sc, 1; Y, 2), [MCl2(bpztcp)(THF)] (M=Sc, 3; Y, 4), and [MCl2(bpzpcp)(THF)] (M=Sc, 5; Y, 6). The H2O adduct of 4, [YCl2(bpztcp)(H2O)] (7), was formed when a solution of 4 was allowed to stand at room temperature in the presence of moisture. Complexes 1-7 adopt a pseudo-octahedral structure with heteroscorpionate ligands kappa2-NNeta5-Cp coordinated to the metal through the cyclopentadienyl group and two imino nitrogens of pyrazole rings. The alkyl heteroscorpionate scandium and yttrium complexes recently reported by our group, [M(CH2SiMe3)2(bpzcp)], react with 2,6-dimethylphenol and 3,5-dimethylphenol to give the bis(aryloxide) derivatives [M(OAr)2(bpzcp)] (M=Sc, OAr=2,6-dimethylphenoxide, 8; M=Y, OAr=2,6-dimethylphenoxide, 9; M=Y, OAr=3,5-dimethylphenoxide, 10). Complex 9 underwent an interesting hydrolysis process to give the tetranuclear complex [{Y(bpzcp)}(micro-OH)2(micro3-OH){Y(OAr)2}]2 (11). Variable-temperature 1H NMR experiments on 9 and 10 revealed a rapid fluxional exchange between coordinated and noncoordinated pyrazolyl rings, producing interconversion between the two enantiomers in which the scorpionate ligand can be coordinated in a kappa1-Neta5-Cp form. The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structures of 2, 7, and 11 were also established. Complexes 1 and 2 are active olefin polymerization catalysts after activation with methylaluminoxane. These compounds gave atactic polystyrenes with narrow molecular weight distribution (Mn/Mw 1.26-1.91) and with low molecular weights.

The reaction of bis(3,5-di-tert-butylpyrazol-1-yl)methane (bdtbpzm) with BunLi and carbodiimide derivatives, namely, N,N′-diisopropyl and 1-tert-butyl-3-ethyl carbodiimides, gives rise to the new sterically hindered lithium acetamidinate [Li(tbptamd)(THF)] (1) [tbptamd = N-ethyl-N′-tert-butylbis(3,5-di-tert-butylpyrazol-1-yl)acetamidinate] and [Li(pbptamd)(THF)] (2) [pbptamd = N,N′-diisopropylbis(3,5-di-tert-butylpyrazol-1-yl)acetamidinate]. Subsequent hydrolysis of 1 and 2, and the recently reported heteroscorpionate lithium salts [Li(tbpamd)(THF)] [tbpamd = N-ethyl-N′-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] and [Li(pbpamd)(THF)] [pbpamd = N,N′-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] with NH4Cl/H2O in ether cleanly affords the corresponding amidine ligands Htbpamd (3), Hpbpamd (4), Htbptamd (5), and Hpbptamd (6) in very good yields. The X-ray diffraction molecular structure of 3 was obtained. Reaction of the amidine-heteroscorpionate ligands 3–6 with 1 equiv of ZnR′2 proceeds...

The reaction of the heteroscorpionate lithium salts [Li(tbpamd)(THF)] [tbpamd = N-ethyl-N‘-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] and [Li(pbpamd)(THF)] [pbpamd = N,N‘-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate] with 1 equiv of RMgCl proceeds to give very high yields of the neutral heteroscorpionate alkyl magnesium complexes [Mg(R)(NNN)] (NNN = tbpamd, R = C3H5 1, tBu 2, CH2SiMe3 3; NNN = pbpamd, R = C3H5 4, tBu 5, CH2SiMe3 6). On heating toluene solutions of complexes 1−3, 5, and 6, a ligand redistribution process occurs to give the corresponding 6-coordinated sandwich complexes [Mg(tbpamd)2] (7) and [Mg(pbpamd)2] (8). Interestingly, the allyl derivative 4 can be easily transformed to 8 at room temperature. In addition, the cationic sandwich complex [Mg(tbpamdH)2]Cl2 (9) [tbpamdH = N-ethyl-N‘-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidine] was obtained from 7 by means of a protonation process. Finally, alkyl-containing complexes 1−6 can act as highly effective single-componen...

The preparation of new hybrid scorpionate/cyclopentadienyl ligands in the form of the lithium derivatives [Li(bpzcp)(THF)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopenta...

Preprint The preparation of the first racemic bis(pyrazol-1-yl)methane-based NNCp-donor hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes [Mg(R)(κ2-η5-NNCp)] (1–6) [NNCp = bpztcp, R = Me (1), Et (2), CH2SiMe3 (3); bpzpcp, R = Me (4), Et (5), CH2SiMe3 (6)] and [Zn(R)(κ2-η1-NNCp)] (7–12) [NNCp = bpztcp, R = Me (7), Et (8), CH2SiMe3 (9); bpzpcp, R = Me (10), Et (11), CH2SiMe3 (12)] has been carried out by the reaction of the corresponding racemic NNCp-H-donor scorpionate pro-ligands with Grignard reagents RMgCl, after deprotonation with nBuLi, or directly with ZnR2. The resulting alkyl magnesium complexes (1–6) have been employed in a protonolysis reaction with 2,6-dimethylphenol to yield the aryloxide magnesium complexes [Mg(OAr)(κ2-η5-NNCp)] (13 and 14) [NNCp = bpztcp (13), bpzpcp (14)]. Subsequently, the enantiopure scorpionate pro-ligand (R,R)-bpmycpH (16a) {bpmycpH = 1-{2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1-(2R)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]ethyl}cyclopentadiene} and (R,R)-bpmycp′H (16b) {bpmycp′H = 2-{2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1-(2R)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]ethyl}cyclopentadiene} reacted with RMgCl (after addition of nBuLi) or with ZnR2 to give the single enantiopure complexes [Mg(R)(κ2-η5-R,S-bpmycp)] (17–19) (R = Me (17), Et (18), CH2SiMe3 (19)) {R,S-bpmycp = 2-{2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1-(2S)-2-[(1R)-6,6-[3.1.1]-2-hepten-2-yl]ethyl}cyclopentadienyl} and [Zn(R)(κ2-η1-R,S-bpmycp)] (20–22) (R = Me (20), Et (21), CH2SiMe3 (22)). The structures of these complexes were elucidated by 1H and 13C{1H} NMR spectroscopy, and the X-ray crystal structures of 2, 3, 7 and 21 were also established. These racemic and single enantiopure complexes 1–3, 5–9, 11–14, 19, and 21 can act as single-component initiators for the ring-opening polymerization of rac-lactide under mild conditions. Microstructural analysis of poly(rac-lactide)s revealed that, whereas the myrtenal substituent on the single enantiomerically pure initiator 21 exerts an appreciable influence on the degree of stereoselectivity to produce isotactic-enriched poly(lactide)s with a Pi value up to 0.77, the racemic mixtures of initiators impart more discrete levels of heteroselectivity in the production of PLAs, with a Ps value of 0.72.