A Chloro-Bridged Dimanganese Complex and an Oxo-Bridged Dititanium Complex of a Ditopic Bis(pyrazol-1-yl)borate Ligand

Abstract

The synthesis and crystal structure analysis of the ditopic p-phenylene-bridged bis(pyrazol-1-yl)borate [[p-C6H4(Bpz2tBu)2]Li2] (LLi2; pz=pyrazol-1-yl) is described. A salt metathesis reaction between LLi2 and MnCl2 in THF leads to the dinuclear complex [L[Mn(THF)]2(mu-Cl)2] featuring a central diamond MnII-(mu-Cl)2-MnII core (X-ray crystal structure analysis). Treatment of LLi2 with 2 equiv of [Ti(NMe2)3Cl] gives the dinuclear titanium compound [L[Ti(NMe2)3]2]. Upon reaction of LLi2 with [Ti(NMe2)2Cl2] and water, the mu-oxo-bridged dititanium species [L[Ti(NMe2)Cl]2(mu-O)] is obtained in excellent yield (X-ray crystal structure analysis).

Bridged Dinuclear Tripodal Tris(amido)phosphane Complexes of Titanium and Zirconium as Diligating Building Blocks for Organometallic Polymers

“…[35] The Ti-N bonds of 4b [1.918(4), 1.918(4), 1.926(4) Å] are shorter than those of P(CH 2 N-3,5-Me 2 C 6 H 3 )TiNMe 2 (3b) [1.963(7), 1.941(6), 1.934(6) Å], reflecting the slightly stronger σ-bonding and π-donation from these donors in compound 4b. [36] The 13 C{ 1 H} NMR chemical shift of the ipso carbon atoms bonded directly to the oxygen atoms are at δ = 164.2 and 153.3 ppm, for 4a and 4b, respectively, which reflects how strongly the degree of π-donation from the oxygen donor in these complexes is influenced by the amido donor substituents. [35] The sum of C-P-C bond angles and P···Ti distances in the solid-state structure of complex 4b are similar to those observed in the parent compound P(CH 2 N-3,5-Me 2 C 6 H 3 ) 3 TiNMe 2 (3b); however, the 31 P{ 1 H} NMR chemical shifts in 4a,b of δ = -81.1 and -77.9 ppm, respectively, are significantly different than those of 3a,b, which are δ = -65.6 and -61.6 ppm.…”

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

“…[33][34][35] So far, the main focus was on homoditopic ligand systems consisting of two identical scorpionate units that are bridged by organometallic or aromatic linkers. Replacement of pyrazolyl rings by thioether moieties allows to extend the research to heteroditopic scorpionate ligands in which the two donor sites are no longer the same so that the two coordinated metal centers will show different reactivity.…”

Broadening the Scope of Ancillary Phosphane‐Type Ligands: A Systematic Comparison of PR3, PR2BH3–, and SiR3– and Their Chalcogen Derivatives

“…[60] Using the PF 6 -salt 14PF 6 , we were able to isolate X-ray quality crystals of the compound by gas-phase diffusion of pentane into a solution of [FpSPtBu 3 ]PF 6 (15PF 6 ) in CHCl 3 (Scheme 2).…”

“…Complexes 11I, 12a, and 13 are derived from the phosphane PPh 2 Me, while complexes 15PF 6 , 16b, and 17 are related to the phosphane sulfide SPtBu 3 . A comparison of these two sets of isoelectronic complexes grants insight into the electronic differences between the ligands.…”

“…Selected bond lengths and angles for 15PF 6 , 16b, and 17 are compiled in Table 3. Details of the X-ray crystal structure analyses of these compounds are summarized in Table 6.…”