Synthesis and diverse crystal packing in o-, m- and p-bis(carbonylthioureido)benzenes containing bisferrocenes.

Three bisferrocene-based bis(acylthiourea) positional isomers, namely, 1,2-bis(ferrocenylcarbonylthioureido)benzene (1), 1,3-bis(ferrocenylcarbonylthioureido)benzene (2) and 1,4-bis(ferrocenylcarbonylthioureido)benzene (3), all [Fe(CH)(CHNOS)], have been synthesized via facile nucleophilic addition reactions of 2.3 equivalents of ferrocenoyl isothiocyanate with o-, m- and p-phenylenediamine, respectively. The structures of the three new synthesized isomers were fully characterized by H NMR, C NMR, IR and UV-Vis spectroscopy, elemental analyses and cyclic voltammetry.

Crystal structure of bis-(N-tert-butyl-benzamidinium) hexa-chlorido-zirconate(IV) di-chloro-methane disolvate.

In the Zr(IV) complex anion of the title complex salt, [(C4H9)HNC(C6H5)NH2]2[ZrCl6]·2CH2Cl2, the Zr(IV) cation, located on an inversion centre, is coordinated by six Cl(-) anions in a distorted octa-hedral geometry with Zr-Cl distances in the range 2.433 (2)-2.4687 (19) Å; in the amidinium cation, the dihedral angle between the aromatic ring and [NCN] plane is 43.

Coordination reactions of 2-pyridinecarboxaldehyde-phenylhydrazonatolithium with selected transition metal (Zn, Sn, Fe, Co, Ni and Zr) chlorides and its coupling reaction with dichloromethane.

The reactions of 2-pyridinecarboxaldehyde-phenylhydrazonatolithium C5H4Npy-CH[double bond, length as m-dash]Ni-NaLi(Ph) (abbreviated as Li) with a 1/2 equivalent of anhydrous metal (Zn, Sn, Fe and Co) chlorides or NiCl2(DME) (DME = 1, 2-dimethoxyethane) produced the corresponding mononuclear metal(ii) complexes ( and ), in which each ligand acts as a bidentate ligand and the coordination geometries around the metals are shown to be tetrahedral within the complexes , , and , respectively, and a tetragonal pyramid in the complex . The reaction of Li successively with sodium tert-butoxide and anhydrous ZrCl4 afforded the unanticipated bizirconium complex , in which each monoanionic ligand behaves as a tridentate bridge. Whereas treatment of Li with NiCl2 and then CH2Cl2 led to an interesting methylene-bridged bis(2-pyridyl-phenylhydrazone) compound in moderate yield; a comparative experiment showed that when the Li reacted with CH2Cl2, the coupling compound was also obtained but in very low yield.

Crystal structure of N'-(2,6-di-methyl-phen-yl)benzene-carboximidamide tetra-hydro-furan monosolvate.

The asymmetric unit of the title compound, C15H16N2·C4H8O, contains two amidine mol-ecules (A and B) with slightly different conformations and two tetra-hydro-furan (THF) solvent mol-ecules. In the amidine mol-ecules, the di-methyl-phenyl ring and the NH2 group lie to the same side of the N=C bond and the dihedral angles between the aromatic rings are 54.25 (7) (mol-ecule A) and 58.

Tetra-chlorido-[N (2),N (2')-(di-methyl-silanedi-yl)bis-(N-tert-butyl-3-methyl-benzimid-amid-ato)-κ(2) N (2),N (2')]hafnium(IV).

The symmetric title mol-ecule, [Hf(C26H40N4Si)Cl4], lies about a twofold rotation axis. The Hf(IV) and Si atoms lie on the rotation axis with all other atoms being in general positions. The Hf(IV) atom is six-coordinated by two N atoms from the N (2),N (2')-(di-methyl-silanedi-yl)bis-(N-tert-butyl-3-methyl-benz-imid-amidate) ligand and four Cl(-) ions in a slightly distorted octa-hedral geometry.

N-Cyclo-hexyl-3-methyl-benzamidine.

The title amidine compound, C14H20N2, prepared by a one-pot reaction, is asymmetric as only one N atom has an alkyl substituent. The terminal cyclo-hexyl group connected to the amino N atom is located on the other side of the N-C-N skeleton to the 4-methylbenzene ring and has a chair conformation. The dihedral angle between the phenyl ring and the NCN plane is 47.

Metal (Mg, Fe, Co, Zr and Ti) complexes derived from aminosilyl substituted aminopyridinato ligand: synthesis, structures and ethylene polymerization behaviors of the group 4 complexes.

Lithium N-[(N,N-dimethylamino)dimethylsilyl]-2-pyridylamidate (2) was prepared from the reaction of new compound N-[(N,N-dimethylamino)dimethylsilyl]-2-pyridylamine (1) and LiBu(n). Treatment of the lithium salt (2) with an equal equivalent of MgBr(2)(THF)(2), FeCl(2) and CoCl(2) afforded the corresponding dinuclear complexes , , and , in which metal atoms possess similar trigonal bipyramidal geometries and each ligand functions as a bimetallic bridging binding aminopyridinato moiety with N-donation from the dimethylamino group. While the stoichiometric reaction of with ZrCl(4) gave the mononuclear zirconium complex (6); the seven coordinated zirconium atom adopts a distorted pentagonal bipyramid geometry and the ligand acts as monoanionic η(2)-aminopyridinato moiety with the pendant arm coordinated via N(CH(3))(2).

meso-Bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}iron(II) and the cobalt(II) analogue.

The two title crystalline compounds, viz. meso-bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}iron(II), [Fe(C(12)H(20)NSi)(2)], (II), and meso-bis{η(5)-1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienyl}cobalt(II), [Co(C(12)H(20)NSi)(2)], (III), were obtained by the reaction of lithium 1-[1-(dimethylamino)ethenyl]-3-(trimethylsilyl)cyclopentadienide with FeCl(2) and CoCl(2), respectively. For (II), the trimethylsilyl- and dimethylaminoethenyl-substituted cyclopentadienyl (Cp) rings present a nearly eclipsed conformation, and the two pairs of trimethylsilyl and dimethylaminoethenyl substituents on the Cp rings are arranged in an interlocked fashion.

Chlorido{N-[(diethyl-amino)-dimethyl-sil-yl]anilido-κN}(N,N,N',N'-tetra-methyl-ethane-1,2-diamine-κN,N')cobalt(II).

In the title cobalt(II) compound, [Co(C(12)H(21)N(2)Si)Cl(C(6)H(16)N(2))], the ethane-1,2-diamine donor mol-ecule coordin-ates the metal atom in an N,N'-chelating mode, with Co-N distances of 2.136 (2) and 2.140 (3) Å.

Mononuclear titanium compounds based on the silyl-linked bis(amidinate) ligand: synthesis, characterization and ethylene polymerization.

The mononuclear silyl-linked bis(amidinate) titanium compound 2 was prepared by salt metathesis of 1 and TiCl(4)(thf)(2). Alkylation of 2 with methyllithium gave analogue 3. Both 2 and 3 exhibited a configuration similar to ansa-metallocene and showed good activity towards ethylene polymerization after activation with MAO.

A bulky silyl shift-directed synthesis of a silyl-linked amidinate-amidine and its Zr(IV) complex.

A novel silyl-linked amidinate-amidine monoanionic ligand 3 was synthesized by double additions of PhCN starting from silyl-linked bis(amino) monoanion 2, which underwent an intramolecular Li/H metathesis and double silyl shift. The related Zr(IV) complex 4 was prepared and confirmed by X-ray diffraction revealing a structural rearrangement from its precursor. The mechanisms for the reaction processes have been proposed.

Ammonium benzene-phospho-nate.

In the crystal structure of the title salt, NH(4) (+).[(C(6)H(5))P(O)(2)(OH)](-) or NH(4) (+)·C(6)H(6)O(3)P(-), the N and O atoms inter-act via hydrogen bonds to generate a layer motif. The phenyl rings are stacked above and below this layer, sandwiching the hydrogen-bonded layer.

A convenient route to silyl linked bis(amidinate) ligands and synthesis of group(I) metal derivatives.

A novel type of linked bis(amidinate) ligands (D) were developed successfully. Their lithium derivatives 1-4 were synthesized by treating the silyl-bridged diamines I-IV with two equivalents of LiBu(n) and PhCN in sequence, which underwent a silyl-bridge migration process. In addition, the linked bis(amidinate) configuration proved to be the thermodynamically stable form rather than the mono(amidinate) type by contrasting reaction of I with one equivalent of LiBu(n) and PhCN in sequence.

Intramolecular NMeH Elimination and Fulvene Coupling Leading to Novel Allyl-Bridged Zirconocene and Hafnocene Complexes.

Deprotonation of the aminofulvene 1 with LiCH(SiMe) provides 2, which reacts with MCl (M=Zr or Hf) by intramolecular NMeH elimination and coupling of the fulvene moieties to form complex 3 or 4. This reaction is a useful synthetic pathway to allyl-bridged ansa-metallocenes, especially those with a conjugated 14 π electron system. R'=dimethylamino.