Unusual phosphorus-phosphorus double bond contraction upon mono- and di-auration of a diphosphene.
The diphosphene Mes*P=Mes* (Mes* = 2,4,6-tri-tert-butylphenyl; 1) reacted with 1 or 2 equiv of Au(tht)Cl (tht = tetrahydrothiophene) to produce the stable monoaurated adduct Mes*{AuCl}P=PMes* (2) or diaurated adduct Mes*{AuCl}P=P{AuCl}Mes* (3) respectively. The products were characterized by X-ray crystallography, UV-visible, IR, Raman, and multinuclear NMR spectroscopies, as well as by density functional theory calculations. The crystallographic and Raman spectroscopic data provide physical evidence that the P=P bond grows shorter and increases in strength upon auration; these observations are further examined by DFT calculations for a series of model compounds CH(3){AuCl}(n)P=P{AuCl}(n')CH(3) 1'-3' (n, n' = 0 or 1). Compounds 1-3 represent a rare series of crystallographically characterized diphosphenes bearing zero, one, or two AuCl units on each phosphorus atom, allowing for a systematic analysis of the impact of Lewis acids on the phosphorus-phosphorus double bond.
Partyka
David V
DV
Creative Chemistry, LLC, Cleveland, Ohio 44106, USA.
Washington
Marlena P
MP
Gray
Thomas G
TG
Updegraff
James B
JB
Turner
John F
JF
Protasiewicz
John D
JD
D003198:Computer Simulation; D018360:Crystallography, X-Ray; D006046:Gold / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D050607:Organogold Compounds / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*
D050607:Organogold Compounds; D010720:Phosphines; D010758:Phosphorus; D006046:Gold