| As in past decades, much interest in organotransition metal complexes continues to be motivated by their biochemistry and their potential applications in catalysis, optical, magnetic and electrical materials. Protonolysis reaction is one of the common methods that are used to prepare organotransition metal complexes. The intriguing protonolysis reactivity of a mononuclear Zn adduct towards the three acids and ethanol along with the isolation and structural characterization of a series of organozinc complexes were reported in this thesis. A family of novel stable amidolanthanide alkylthiolates along with a series of mono- and di- substituted bis(trimethylsily)amide Ianthanide(III) chloride complexes were prepared and fully characterized, and their catalytic activities toward the ROP of e-caprolactone were also investigated. They are briefly summarized as follows:1. Protonolysis reactions of [Zn(dmpzm)Et2] (1) with acetic, formic or benzoic acid in different molar ratios gave rise to five mononuclear zinc complexes [ZnEt(dmpzm)(L)] (2: L = OAc; 3: L = HCOO; 8: L = PhCOO) and [Zn(dmpzm)(L)2] (4: L = OAc; 5: L = HCOO), one nonanuclear zinc complex [Zn(μ4-O)2 (ZnEt)6 (μ3-OAc)4(μ'3-OAc)2{Zn(dmpzm)Et}2] (6), and one tetranuclear zinc complex [Zn4(μ4-O)(dmpzm)3Et3] (7). Similar treatment of [Zn(dmpzm)Et2] (1) with EtOH formed a dinuclear zinc complexes [(Zn(dmpzm)Et)2(μ-OEt)][PF6] (9). Analogous reactions of [ZnTp*Et] (10) with acetic acid in different molar ratios gave rise to two mononuclear zinc complexes [ZnTp*Et1/2(OAc)1/2] (11) and [ZnTp*OAc] (12). Compounds 1-12 were characterized by elemental analysis, IR spectra, 1H NMR spectra, and structures of 1, 3, 4, 6-12 were determined by single-crystal X-ray crystallography. In the structures of 1,3, 4 and 8, the central Zn atom is tetrahedrally coordinated by two N atoms of one dmpzm and two C atoms of two Et groups (1), or one C atom of one Et group and one O atom of formate ligand (3), two O atoms of two acetates (4) or O atom of benzoic ligand (8). In the structure of 6, a heptanuclear[Zn(μ4-O)2(ZnEt)6(μ3-OAc)4] core is connected with two [Zn(dmpzm)Et]+ fragments via a pair ofμ'3-OAc ligands. Compound 7 consists of a Zn4(μ4-O) tetrahedron in which three Zn atoms are further saturated by two N atoms from dmpzm ligands and an ethyl group while one Zn center is coordinated by three C atoms from the methylene group of the three dmpzm ligands. Compound 9 isμ-OEt-bridged dimer in which each Zn atom adopts a distorted tetrahedronal coordination. In the structures of 10, 11, 12, the central Zn atom is tetrahedral geometry.2. Protonolysis reactions of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3(Ln=Pr,Nd,Sm,Eu) with equimolar ButSh or EtSH, afforded four neutral binuclear complexes [{(Me3Si)2N}2Ln(μ-SBut]2(13: Ln = Pr; 14: Ln = Nd; 15: Ln = Sm; 16: Ln = Eu) and four anionic tetranuclear complexes [Li(THF)4][{(Me3Si)2N}4Ln4-(μ4-SEt)(μ-SEt)8] (17: Ln = Pr; 18: Ln = Nd; 19: Ln = Sm; 20: Ln = Eu). Compounds 13-20 were characterized by elemental analysis, IR spectra,1H NMR spectra and single-crystal X-ray diffraction. their catalytic properties were also investigated. Compounds 13-16 are thiolate-bridged dimers in which each Ln atom adopts a distorted tetrahedral coordination. Compounds 17-20 contain a Ln4 square plane, which is capped by aμ4-SEt- ligand. The edges of the square are bridging by four pairs of SEt- ligands on both sides of the Ln4 plane. Each Ln atom has a distorted octahedral geometry.3. Protonolysis reactions of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3(Ln=Pr,Nd,Sm,Eu) with four equiv. of 4,6-dimethyl-2-pyrimidinethiol (DMPYSH), afforded five anionic mononuclear complexes Li[Ln(DMPYS)4] (21: Ln = Pr; 22: Ln = Nd; 23: Ln = Sm; 24: Ln = Eu) and [PPh4][Sm(DMPYS)4] (25). Insertion of PhNCO into the Ln-S bond of 21-24 formed an unexpected product PhNHCOSC6N2H7 (26). Compounds 21-26 were characterized by elemental analysis, IR spectra, 1H NMR spectra and single-crystal X-ray diffraction, their thermolysis properties were also investigated. In the structures of the anions of 21-25, the metal center is surrounded by four S and four N atoms of theη2-DMPYS ligands, forming a distorted dodecahedral arrangement.
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