Group 10 and 11 metal boratranes (Ni, Pd, Pt, CuCl, AgCl, AuCl, and Au+) derived from a triphosphine-borane.
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.
Sircoglou
Marie
M
Laboratoire Hétérochimie Fondamentale et Appliquée (UMR-CNRS 5069) and Structure Fédérative Toulousaine en Chimie Moléculaire (FR 2599), Université Paul Sabatier, 118, route de Narbonne, F-31062 Toulouse Cedex 09, France.
Bontemps
Sébastien
S
Bouhadir
Ghenwa
G
Saffon
Nathalie
N
Miqueu
Karinne
K
Gu
Weixing
W
Mercy
Maxime
M
Chen
Chun-Hsing
CH
Foxman
Bruce M
BM
Maron
Laurent
L
Ozerov
Oleg V
OV
Bourissou
Didier
D
D001880:Boranes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry; D006046:Gold / Q000737:chemistry; D017612:Gold Compounds / Q000737:chemistry; D007854:Lead / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory; D018030:Silver Compounds / Q000737:chemistry
D001880:Boranes; D017612:Gold Compounds; D008670:Metals; D009942:Organometallic Compounds; D010720:Phosphines; D018030:Silver Compounds; C038016:gold chloride; D007854:Lead; D010165:Palladium; D006046:Gold; D003300:Copper; D009532:Nickel; C028419:cuprous chloride; C037548:silver chloride