Evidence for a Strong trans Influence of the Diboran(4)yl Ligand

Abstract

Diboran(4)yl Pt(II) complexes: Selective oxidative addition of one B-I bond in B(2)(NMe(2))(2)I(2) to [Pt(PiPr(3))(2)] affords a trans-diboran(4)yl platinum(II) complex (see scheme; Ar(F) = 3,5-(CF(3))(2)C(6)H(3)). Comparison of its Pt-I bond lengths and the Pt-Br bond lengths of its bromine analogue with related species served to evaluate the trans influence of the ligand. The trans influence enabled facile halide abstraction to generate T-shaped 14-electron diboran(4)yl platinum(II) complexes.

Boranediyl‐ and Diborane(4)‐1,2‐diyl‐Bridged Platinum A‐Frame Complexes

“…The complex displays a strong distortion of its A‐frame geometry, with P1‐Pt1‐Pt2‐P2 and P3‐Pt1‐Pt2‐P4 torsion angles of around 27° (see side‐view of 4 in Figure ). It is noteworthy that, whereas the B−B bond in [ μ ‐{B 2 (NMe 2 ) 2 }{(PEt 3 ) 2 PtI} 2 ] (1.783(7) Å) is significantly longer than that of the B 2 I 2 (NMe 2 ) 2 precursor (1.684(6) Å), the B−B bond in 4 (1.687(8) Å) is of a similar length to that in B 2 Br 2 (NMe 2 ) 2 (1.682(16) Å), the elongation likely being prevented by the geometry imposed by the A‐frame. Like complexes 2‐Y complex 4 proved very unstable in solution and in the solid state, decomposing to 2‐NMe 2 and ultimately to 3 .…”

Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse

“…Platinum­(II) diboryl complexes could be formed from the oxidative addition of B–X bonds of B 2 X 2 (NMe 2 ) 2 at zerovalent platinum centers . These diboryl groups were found to have a strong trans influence, resulting in a lengthening and labilizing effect on trans -Pt–Br and Pt–I bonds compared to the dihaloboryl analogues .…”

Trans Influence of Boryl Ligands in CO2 Hydrogenation on Ruthenium Complexes: Theoretical Prediction of Highly Active Catalysts for CO2 Reduction

“…All the Ru-H bonds on the complexes with these trans non-boryl ligands are shorter than that on the Ru(PNP)(CO)H 2 complex, thus we deduce that the hydride on these complexes will be less active for CO 2 hydrogenation than that on the Ru(PNP)(CO)H 2 complex. Some studies in the literature have reported that the boryl ligands have a very strong trans influence [29][30][31][32][33]. Thus, we examined the trans influence of some usual boryl ligands.…”