A Density Functional Study of the Dimerization of Phosphaalkynes in the Presence of Transition Metal Fragments

✍ Scribed by Steven Creve; Minh Tho Nguyen; Luc G. Vanquickenborne

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 402 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199908)1999:8<1281::aid-ejic1281>3.0.co;2-n

✦ Synopsis

The dimerization of phosphaalkynes (R-CϵP, R = H, Me, tBu)

[H 2 C 2 P 2 ] systems. In an attempt to address the exciting controversy and uncertainty about phosphaalkyne without and with the presence of transition metal fragments, including CpCo (Cp = cyclopentadienyl) and COT-Ti (COT = dimerization, a number of dimer formation mechanisms proposed in the literature have been examined. Some new cyclooctatetraene), has been probed using density functional theory calculations (B3LYP with different basis sets). MP2 and plausible intermediates have also been identified. and CCSD(T) calculations were also performed for the With Zr or Hf as metallic center, however, a 1,3-diphos-Scheme 2. Observation of 1,3-DPCB in Fe and Ni complexes However, no clear-cut evidence has been found yet proving or disproving that the mechanisms of formation of other complexes (such as shown in Schemes 1 and 2) also [a