Group 10 and 11 Metal Boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au⁺) Derived from a Triphosphine−Borane

Abstract

The ambiphilic triphosphine-borane ligand 1 {TPB = [o-iPr2P-(C6H4)3B} readily coordinates to all group 10 and 11 metals to afford a complete series of metal boratranes (TPB)[M] 2-8 (2: M = Ni, 3: M = Pd, 4: M = Pt, 5: M = CuCl, 6: M = AgCl, 7: M = AuCl, 8: M = Au+). Spectroscopic and structural characterization unambiguously establishes the presence of M-B interactions in all of these complexes. The first evidence for borane coordination to copper and silver is provided, and the Au-->B interaction is shown to persist upon chloride abstraction. Experimental and theoretical considerations indicate that the M-->B interaction is strongest in the Pt and Au complexes. The influence of the oxidation state and charge of the metal is substantiated, and the consequences of relativistic effects are discussed. The coordination of the sigma-acceptor borane ligand is found to induce a significant bathochromic shift of the UV-vis spectra, the Ni, Pd, and Pt complex presenting strong absorptions in the visible range. In addition, all of the group 10 and 11 metal boratranes adopt C3 symmetry both in the solid state and in solution. The central M-->B interaction is found to moderately influence the degree of helicity and configurational stability of these three-bladed propellers, and DFT calculations support a dissociative pathway for the inversion process.

Thermally stable N2 and H2 adducts of cationic nickel(ii)

“…A nickel tris(phosphino)boratrane complex, [TP iPr B]Ni, has been reported by Bourissou and co-workers 24 and can be regarded as …”

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

“…An example of the latter is a series of three copper boratranes with Cu reduced from cationic(1+) to neutral to anionic(1−) [153]. The strength of a TM LB interaction increases more profoundly down a group [154]. An example [150] of a practically single-bond order is in Fig.…”

“…The supported TM → Z complexes include bis-or tris-(methimazolyl)boranes and phosphine boranes, with main contributions from the groups of Hill [324], Parkin [325], Bourissou [154], and more recently of Mösch-Zanetti [326] and Nakazawa [327]. Contemporary examples of unsupported structurally characterized TM → Z complexes are chronicled in a remarkable series of articles by Braunschweig and co-workers utilizing the electron-rich, two-coordinate Pt(PCy 3 ) 2 (Cy = cyclohexyl) or Pt(PCy 3 )(IMes) [IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazole-2-ylidene] fragments.…”

Stepwise cure and properties of silicone resin for high‐ultraviolet‐transmission optical elements

“…Firstly, the absorption band can easily be generated from the light-energy absorption of Pt catalyst in UV region. 17,44 Second, even the mirror reflection from the sheet surface plays a role in decreasing UV transmittance.…”