APPLICATION OF THE LIGAND POLYHEDRAL MODEL TO THE FLUXIONALITY OF FE3(CO)10(CNCF3)(L) (L=CO,PME3,PET3,P(OME)3,P(OET)3

The fluxionality observed for the triiron carbonyl clusters Fe3(CO)10(CNCF3)(L) (L = CO, PMe3, PEt3, P(OMe)3, P(OEt)3) has been reassessed in the light of the ligand polyhedral model

FLUXIONAL BEHAVIOR OF THE CARBONYLS [M3(CO)12] (M = FE, RU OR OS)

A study of the crystal structures of the carbonyls [M3(CO)12] (M = Fe, Ru or Os) and a series of their derivatives [M3(CO)12-nLn] has revealed good evidence in support of the hypothesis that the mechanism of ligand fluxionality goes via the intermediacy of an anticubeoctahedral complementary geometry. Several examples of systems with an icosahedral distribution of ligands and quasi-D3 symmetry have been identified providing additional support for our earlier suggestion that a second isomer of [Fe3(CO)12], which exists in solution, adopts a similar D3 structure

Redetermination of the structure of potassium tetranitropalladate(II)

K2Pd(NO2)4, M(r) = 368.58, monoclinic, P2(1)/c, a = 9.254 (5), b = 12.747 (3), c = 7.805 (2) angstrom, beta = 96.43 (2)-degrees V = 914.9 angstrom3 [from setting angles for 14 0kl and 12 h0l data, 20 = 18-340, lambda(Mo Kalpha) = 0.71073 angstrom], Z = 4, D(x) = 2.676 Mg m-3, mu = 2.95 mm-1, F(000) = 704, T = 295 K, R = 0.031 for 2327 unique observed reflections. There are two crystallographically independent Pd(NO2)42- ions, each square planar with symmetry 1BAR (C(i)); Pd-N distances are in the range 2.018 (2)-2.047 (2) angstrom

Fragmentation of transition metal carbonyl cluster anions: Structural insights from mass spectrometry

The anionic clusters [HOs5-(Co)(15)](-), [PtRu5C(CO)(15)](2-), [Os10C-(CO)(24)](2-), [Os-17(CO)(36)](2-), [Os-20(CO)(40)](3-) [Co6C(CO)15]2-, [Pt3Ru10C2-(CO)(32)](2-) and [Pd6Ru6(CO)(24)](2-) have been analysed by energy-dependent electrospray ionisation mass spectrometry (EDESI-MS). Three main features have emerged. Firstly, carbonyl ligands are fragmented from clusters with compact metal cores in an orderly fashion, with each of the ions generated by CO loss having approximately equal intensity. Secondly. electron autodetachment takes place in multiply charged anionic clusters. but only after elimination of a large proportion of their carbonyl ligands. Thirdly, clusters with open metal cores do not undergo CO loss in an orderly fashion. but certain peaks are considerably less intense. The appearance of these low-intensity peaks is believed to signify polyhedral core rearrangements, with open clusters folding to form more compact geometries. In some cases. the gas-phase transformations observed by EDESI-MS mirror those that are known to take place in solution