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Metal−Metal Interactions in Thallium(I)/Platinum(II) Compounds Involving a Chelating Dicarbene and Various Auxiliary Ligands

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posted on 23.01.2006, 00:00 by Jay R. Stork, Marilyn M. Olmstead, James C. Fettinger, Alan L. Balch
Reaction of TlINO3 and (C4H10N4)PtII(mnt) or (C4H10N4)PtII(dmg-H) [mnt = maleonitriledithiolate, dmg-H = dimethylglyoximate dianion] in dilute, aqueous KOH yielded adducts of TlI and the conjugate bases of the platinum(II) compounds. The compound TlI[(C4H9N4)PtII(dmg-H)]·5H2O forms as dimers with close TlI···PtII separations of 3.0843(5) Å, while TlI[(C4H9N4)PtII(mnt)] has much longer TlI···PtII separations of 3.4400(2) Å and forms loosely associated, helical coordination polymers. The new compounds are compared with the red and yellow polymorphs of TlI[(C4H9N4)PtII(CN)2], and the influences of crystal packing forces, Coulombic interactions, and hydrogen bonding on supramolecular structures and TlI···PtII separations are discussed.