Guangcai Bai

Base‐Assisted Formation of Organozirconium Oxides with the [Zr6(μ6‐O)(μ3‐O)8] Core Structure

KH and the two-phase system liquid ammonia/toluene provide the basis for a new method for the synthesis of organozirconium oxides such as [{(EtMe4 C5 )Zr}6 (μ6 -O)(μ3 - O)8 ]⋅C7 H8 (the central inorganic core of the cluster is shown). Altering the solvent to mesitylene has no influence on the core structure of the resulting organozirconium oxide.

Syntheses and structures of the first examples of zinc compounds with bridging fluorine and hydrogen atoms

The first examples of zinc compounds with bridging fluorine and hydrogen atoms [{HC(CMeNAr)2}Zn(μ-X)]2 (Ar = 2,6-Me2C6H3, X = F, 8; X = H, 9) have been synthesised and structurally characterised.

Bis(arylimido) Molybdenum(VI) Amidinate and Guanidinate Complexes; Molecular Structures of [(ArN)2MoMe{N(Cy)C[N(i-Pr)2]N(Cy)}] (Ar = 2,6-i-Pr2C6H3; Cy = Cyclohexyl) and [(2,6-i-Pr2C6H3N)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2]

The reaction of [(ArN)2MoCl2] · DME (Ar = 2,6-i-Pr2C6H3) (1) with lithium amidinates or guanidinates resulted in molybdenum(VI) complexes [(ArN)2MoCl{N(R1)C(R2)N(R1)}] (R1 = Cy (cyclohexyl), R2 = Me (2); R1 = Cy, R2 = N(i-Pr)2 (3); R1 = Cy, R2 = N(SiMe3)2 (4); R1 = SiMe3, R2 = C6H5 (5)) with five coordinated molybdenum atoms. Methylation of these compounds was exemplified by the reactions of 2 and 3 with MeLi affording the corresponding methylates [(ArN)2MoMe{N(R1)C(R2)N(R1)}] (R1 = Cy, R2 = Me (6); R1 = Cy, R2 = N(i-Pr)2 (7)). The analogous reaction of 1 with bulky [N(SiMe3)C(C6H5)C(SiMe3)2]Li · THF did not give the corresponding metathesis product, but a Schiff base adduct [(ArN)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2] (8) in low yield. The molecular structures of 7 and 8 are established by the X-ray single crystal structural analysis. Bis(arylimido) Molybdan(VI) Amidinat und Guanidinat Komplexe; Strukturbestimmungen von [(ArN)2MoMe{N(Cy)C[N(i-Pr)2]N(Cy)}] (Ar = 2,6-i-Pr2C6H3; Cy = Cyclohexyl) und [(2,6-i-Pr2C6H3N)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2] Die Umsetzungen von [(ArN)2MoCl2] · DME (Ar = 2,6-i-Pr2C6H3) (1) mit Lithium- Amidinaten oder Guanidinaten lieferten Molybdan(VI) Komplexe [(ArN)2MoCl{N(R1)C(R2)N(R1)}] (R1 = Cy (Cyclohexyl), R2 = Me (2); R1 = Cy, R2 = N(i-Pr)2 (3); R1 = Cy, R2 = N(SiMe3)2 (4); R1 = SiMe3, R2 = C6H5 (5)) mit funffach koordinierten Molybdan Atomen. Durch die Reaktion von 1 und 2 mit MeLi wurden die entsprechenden Methylate [(ArN)2MoMe{N(R1)C(R2)N(R1)}] (R1 = Cy, R2 = Me (6); R1 = Cy, R2 = N(i-Pr)2 (7)) erhalten. In einer analogen Reaktion von 1 mit dem sterisch anspruchsvollen Lithiumsalz des 1-Azaallylliganden [N(SiMe3)C(C6H5)C(SiMe3)2]Li · THF konnte nicht das entsprechende Metatheseprodukt, sondern ein Addukt an die Schiffsche Base in geringer Ausbeute dargestellt werden [(ArN)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2] (8). 7 und 8 wurden durch Einkristallrontgenstrukturanalysen charakterisiert.

New synthetic route for organic polyoxometallic clusters: synthetic and structural investigations on the first dumb-bell shaped polyoxozirconium hydroxide with the [Zr9(μ5-O)2(μ3-O)4(μ-O)4(μ-OH)8] core structure

A new route for organic polyoxometallic clusters describes the first dumb-bell-like organic polyoxozirconium hydroxide [[(Cp*Zr)4(mu5-O)(mu3-O)2(mu-OH)4]2Zr(mu-O)4] x 2C7H8 (2; Cp* = C5Me5) involving the treatment of the Brønsted acidic organozirconium hydroxide [(Cp*Zr)6(mu4-O)(mu-O)4(mu-OH)8] x 2C7H8 (1) with organozirconium compounds.

The formation of an imidozirconium compound by migration of the imido group from phosphorus to zirconium

The η3/η1-bis(tert-butylamido)cyclodiphosph(III)azane zirconium chloride (η3-L)(η1-LH)ZrCl [1; L = (PNtBu)2(NtBu)2] has been synthesized from the reaction of ZrCl4 with LH2 and nBuLi in toluene. Further reaction of 1 with K–Na alloy in toluene leads to the cleavage of two P–N bonds of the η3-L ligand and the migration of the NtBu group from P to Zr, with the formation of the amidoimidozirconium potassium complex [(η1-LH)ZrNtBu{(NtBu)2PPNtBu}{K·(η6-C7H8)}·0.5C7H8] (2). The molecular structures of 1 and 2 have been determined by X-ray diffraction. In the crystalline state of 2 an η1-L ligand, an imido moiety (NtBu) and two amido nitrogen atoms [η2-(NtBu)2PPNtBu] bind to the zirconium center, and the coordination sphere of K is occupied by three amido nitrogen atoms [η3-(NtBu)2PPNtBu], an η6-C7H8 molecule and two Me groups.