Article

Journal of Cluster Science

, Volume 12, Issue 1, pp 61-74

First online:

Synthesis, Electrochemistry and Crystal Structure of the [Ni36Pt4(CO)45]6− and [Ni37Pt4(CO)46]6− Hexaanions

  • Francesco DemartinAffiliated withDipartimento di Chimica Strutturale e Stereochimica Inorganica
  • , Fabrizia Fabrizi de BianiAffiliated withDipartimento di Chimica
  • , Cristina FemoniAffiliated withDipartimento di Chimica Fisica ed Inorganica, Università di Bologna
  • , Maria Carmela IapalucciAffiliated withDipartimento di Chimica Fisica ed Inorganica, Università di Bologna
  • , Giuliano LongoniAffiliated withDipartimento di Chimica Fisica ed Inorganica, Università di Bologna
  • , Piero MacchiAffiliated withDipartimento di Chimica Strutturale e Stereochimica Inorganica
  • , Piero ZanelloAffiliated withDipartimento di Chimica

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Abstract

The [Ni36Pt4(CO)45]6- and [Ni37Pt4(CO)46]6- clusters have been obtained in mixture upon reaction in acetonitrile of [Ni6(CO)12]2- salts with K2PtCl4 in a 2.5:1 molar ratio. The two hexaanions were indistinguishable by spectroscopic techniques. Crystallization of their trimethylbenzylammonium salts led to crystals of composition 0.5[NMe3CH2Ph]6[Ni36Pt4(CO)45]-0.5[NMe3CH2Ph]6[Ni37Pt4(CO)46]·C3H8O, hexagonal,space group P63 (No. 173), a=17.853(9), c=27.127(13) Å, Z=2; final R=0.057. The metal core of the [Ni36Pt4(CO)45]6- anion consists of a Pt4 tetrahedron fully encapsulated in a shell of 36 Ni atoms belonging to a very distorted and incomplete ν5 tetrahedron. The [Ni37Pt4(CO)46]6- hexaanion derives from the former by capping the unique triangular face of the metal polyhedron with an additional Ni(CO) fragment. The [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- mixture is rapidly degraded to the known [Ni9Pt3(CO)21]4- cluster by exposure to carbon monoxide. Its reaction with protic acids initially affords the corresponding [H6-nNi36Pt4(CO)45]n--[H6-nNi37Pt4(CO)46]n- (n=5, 4) derivatives, and eventually leads to rearrangement to the known [H6-n Ni38Pt6(CO)48]n- species. Both [Ni36Pt4(CO)45]6--[Ni37Pt4(CO)46]6- and [HNi36Pt4(CO)45]5--[HNi37Pt4(CO)46]5- mixtures have been chemically and electrochemically reduced to their corresponding [Ni36Pt4(CO)45]n--[Ni37Pt4(CO)46]n- (n=7–9) and [HNi36Pt4(CO)45]n--[HNi37Pt4(CO)46]n- (n=6–8) mixtures.

carbonyl nickel platinum