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In the title compound, di-μ-cyanato-1:2κ²N:C;2:3κ²C:N-di­cyanato-2κ²C-bis­(1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne)-1κ6O;3κ6O-1,3-dipotassium(I)-2-platinum(II), [K2Pt(CN)4(C12H24O6)2] or [K(18-crown-6)]2·[Pt(CN)4], two trans-orientated cyano groups of the square-planar [Pt(CN)4]2− dianion (Pt· · ·Pt site symmetry 1) bind to one potassium ion each, which are additionally coordinated by the six O atoms of 18-crown-6. No PtPt inter­actions occur in the crystal, but very weak Pt· · ·H contacts (2.79 Å) are observed. [ABSTRACT FROM AUTHOR]

In the title compound, di-μ-cyanato-1:2κ²N:C;2:3κ²C:N-di­cyanato-2κ²C-bis­(1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne)-1κ6O;3κ6O-1,3-dipotassium(I)-2-platinum(II), [K2Pt(CN)4(C12H24O6)2] or [K(18-crown-6)]2·[Pt(CN)4], two trans-orientated cyano groups of the square-planar [Pt(CN)4]2− dianion (Pt· · ·Pt site symmetry 1) bind to one potassium ion each, which are additionally coordinated by the six O atoms of 18-crown-6. No PtPt inter­actions occur in the crystal, but very weak Pt· · ·H contacts (2.79 Å) are observed. [ABSTRACT FROM AUTHOR]

To access the hitherto almost unknown class of clustered transition metal carbonyl cations, the trimetal dodecacarbonyls M 3 (CO) 12 (M = Ru, Os) were reacted with the oxidant Ag + [WCA] - , but yielded the silver complexes [Ag{M 3 (CO) 12 } 2 ] + [WCA] - (WCA = [Al(OR F ) 4 ] - , [F{Al(OR F ) 3 } 2 ] - ; R F = -OC(CF 3 ) 3 ). Addition of further diiodine I 2 to increase the redox potential led for M = Ru non-specifically to divalent mixed iodo-Ru II -carbonyl cations. With [NO] + , even the N-O bond was cleaved and led to the butterfly carbonyl complex cation [Ru 4 N(CO) 13 ] + in low yield. Obviously, ionization of M 3 (CO) 12 with retention of its pseudo-binary composition including only M and CO is difficult and the inorganic reagents did react non-innocently. Yet, the radical cation of the commercially available perhalogenated anthracene derivative 9,10-dichlorooctafluoroanthracene (anthracene Hal ) is a straightforward accessible innocent deelectronator with a half-wave potential E 1/2 of 1.42 V vs. Fc 0/+ . It deelectronates M 3 (CO) 12 under a CO atmosphere and leads to the structurally characterized cluster salts [M 3 (CO) 14 ] 2+ ([WCA] - ) 2 including a linear M 3 chain. The structural characterization as well as vibrational and NMR spectroscopies indicate the presence of three electronically independent sets of carbonyl ligands, which almost mimic M(CO) 5 , free CO and even [M(CO) 6 ] 2+ in one and the same cation., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)