Abstract
The stable tetrahedral derivative Ni(PF(3))(4) is reported to generate binuclear Ni(2)(PF(3))(n) ions in its mass spectrum emerging from ion-molecule reactions. Theoretical studies on such binuclear complexes indicate Ni(2)(PF(3))(7) to be energetically unfavorable with respect to decomposition into Ni(PF(3))(4) + Ni(PF(3))(3). However, viable rather unsymmetrical structures with two PF(3) bridges for Ni(2)(PF(3))(n) (n = 6, 5, 4) are reported here as well as a triply semibridged Ni(2)(PF(3))(5) structure. The nickel-nickel distances in these Ni(2)(PF(3))(n) derivatives suggest a formal double bond (2.51 A), a formal triple bond (2.26 A), and a formal double bond (2.34 A) for n = 6, 5, and 4, respectively. The mononuclear Ni(PF(3))(n) derivatives are predicted to have tetrahedral, trigonal planar, and bent (139 degrees ) structures for n = 4, 3, and 2, respectively.
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