Syntheses and Structures of Metallocene Methyltrihydroborate Derivativies:  Cp₂ZrCl{(μ-H)₂BHCH₃}, Cp₂Zr{(μ-H)₂BHCH₃}₂, and Cp₂Ti{(μ-H)₂BHCH₃}

Abstract

In reactions of zirconocene dichloride, Cp(2)ZrCl(2), with 1 equiv and an excess amount of LiBH(3)CH(3), the methyltrihydroborate complexes, Cp(2)ZrCl[(mu-H)(2)BHCH(3)], 1, and Cp(2)Zr[(mu-H)(2)BHCH(3)](2), 2, were isolated. The reaction of titanocene dichloride, Cp(2)TiCl(2), with an excess amount of LiBH(3)CH(3) produced the monosubstituted methyltrihydroborate complex, Cp(2)Ti[(mu-H)(2)BHCH(3)], 3. The titanium was reduced from Ti(IV) to Ti(III), producing a 17-electron, paramagnetic titanocene complex. Under a dynamic vacuum at room temperature, compound 2 decomposed and produced the zirconium hydride compound Cp(2)ZrH[(mu-H)(2)BHCH(3)]. Single crystal X-ray structures of 1, 2, and 3 were determined. Crystal data for 1: space group P2(1)/c, a = 13.7921(3) A, b = 13.4227(3) A, c = 13.0868(3) A, beta = 91.6448(12) degrees, Z = 8. Crystal data for 2: space group Pna2(1), a = 15.2949(4) A, b = 9.3417(2) A, c = 9.3211(2) A, Z = 4. Crystal data for 3: space group Fmm2, a = 9.1795(3) A, b = 13.0993(5) A, c = 8.8520(3) A, Z = 4.

A novel photoluminescent Ag–terpyridyl complex: one-dimensional linear metal string with double-helical structure

“…In the junction of two tetranuclear cations, face-to-face p-stacking interactions (centroid-centroid distances of 3.733 and 3.777 Å ) between adjacent pyridine rings are responsible for the stabilization of the infinite spiral structure. The silver string is strictly linear and forms a molecular wire, which potentially acts as an electronic material [24].…”

Synthesis and Structure of MnCl2(HDpyF) (HDpyF =N,N′-di(2-pyridyl)formamidine): New Crystallographic Disorder and Bonding Mode of the HDpyF Ligand

“…The twist between the two pyridyl rings in most of the polydentate nitrogen ligands were ascribed to the H···H repulsion, I, 6,7 or the p-p stacking between the aromatic …”

Syntheses and characterizations of group 6 metal cyanotrihydroborate complexes

“…These chemical shifts and coupling constants are consistent with those found in NaBH 3 CN ()43.5 ppm, J B-H ¼ 89.0 ppm) [7] and those reported in the cyanotrihydroborate complexes [2d,4a,4b,5b], which suggest that the coordination of the [BH 3 CN] À ligand to the metal is through a nitrogen atom. Although the boron chemical shifts of the cyanohydroborate-bridged complexes have not been reported, significant changes have been observed in other organohydroborate ligands upon coordinating of the B-H hydrogen to the metal [8]. The narrow ranges of the chemical shifts of the boron and the BH 3 hydrogen atoms in complexes 1, 2, 3, and 4 indicate little change of the electron density on the boron and the hydrogen nuclei upon coordination of the nitrogen to the metal.…”