Abstract
Reactions of the tris(2-diisopropylphosphino-N-pyrrolyl)alane ligand 1 (AlP3) furnished an (AlP3)Pt complex 2, which was determined to possess a Pt → Al interaction. Compound 2 reacted with CO to form the corresponding isolable adduct 3. Exposure of 2 to H2 or HD in solution resulted in the observation of equilibrium binding which favors 2 at room temperature, and more strongly favored the adducts 2-H2 and 2-HD at −80 °C. The presence of the Pt–H2/HD moieties is supported by low temperature NMR determination of 1JPPt = 323 Hz (2-H2) and 1JHD=34 Hz (2-HD), ostensibly the first examples of Pt dihydrogen complexes with a trigonal bipyramidal geometry. The reaction of 1 with (tht)AuCl (tht = tetrahydrothiophene) generated compound 4 with loss of tht. An XRD study of 4 revealed the transfer of chloride to Al and a long separation between Al and Au coordinated by the three phosphine arms. Abstraction of chloride from 4 did not lead to a tripodal structure isoelectronic to 2, but (according to solution NMR evidence) instead to the transfer of one of the phosphine arms to Al from Au in compound 5.
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