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The title compound, (C27H26P3)[AlCl4]·CH2Cl2, was isolated from a mixture containing the triphosphenium ion and its protonated derivative. The central cation ring is non‐planar, as in the analogous hexachlorostannate (though the structures are not isomorphous), and the P—P distances are intermediate between those typical for single and double bonds.

The title saccharinate complexes, aqua[1,2‐benzisothiazol‐3(2H)‐onato 1,1‐dioxide‐N]bis(1,10‐phenanthroline‐N,N′)man­ganese(II) 1,2‐benz­isothia­zol‐3(2H)‐onate 1,1‐dioxide,[Mn(C7H4NO3S)(C12H8N2)2(H2O)](C7H4NO3S), and aqua[1,2‐benz­iso­thiazol‐3(2H)‐onato 1,1‐dioxide‐N]­bis­(2,2′‐bi­pyri­dine‐N,N′)­cobalt(II) 1,2‐benz­iso­thia­zol‐3(2H)‐onate 1,1‐di­oxide, [Co­(C7H4NO3S)­(C10H8N2)2­(H2O)]­(C7H4NO3S), have been prepared and their crystal structures determined at 150 K. The structure of the manganese complex consists of repeated alternating [Mn(phen)2(sac)(H2O)]+ cations and non‐coordinated saccharinate anions. The water molecule, bound to manganese as part of a slightly distorted octahedral arrangement, is hydrogen bonded to an O atom of the SO2 group in the saccharinate counter‐ion. In contrast, the cobalt complex has one pseudo‐octahedral [Co(bipy)2(sac)(H2O)]+ cation, with the cobalt‐bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion.

The first transition metal complexes of cyclic triphosphenium ions have been unequivocally identified in solution by (31)P NMR spectroscopy. The ligands coordinate to platinum(II) via the central phosphorus atom, but only when at least one of the outer phosphorus atoms has non-aromatic substituents. Depending on the system, either trans- (the kinetic reaction product) and/or cis- (the thermodynamic reaction product) complexes are formed. The (1)J coupling constants between (195)Pt and the central phosphorus atom of the CTI (P(A)) are small for both cis- and trans-isomers, between 900 and 1300 Hz, whereas other phosphanes in these complexes derived from the platinum(II) starting material show normal (1)J(PtP) values. These results suggest a possible long P-Pt bond between the overall positively charged ligand and the platinum(II) cation. Calculations including predicted (31)P NMR shifts for the CTIs and their Pt(II) complexes largely support our experimental findings.