Synthesis and bonding in the diamagnetic dinuclear tantalum(IV) hydride species ([P2N2]Ta)(2)(mu-H)(4) and the paramagnetic cationic dinuclear hydride species ([P2N2]Ta)(2)(mu-H)(4)I-+(-) ([P2N2] = PhP(CH2SiMe2NSiMe2CH2)(2)PPh): The reducing ability of

The controlled reaction of the Ta(V) trimethyl species [P2N2]TaMe3, where [P2N2] = PhP(CH2SiMe2NSiMe2CH2)(2)PPh, under 0.5 atm of hydrogen gas produces a partially hydrogenated Ta(V) species, [P2N2]TaMe2(H), of unknown structure. Under 4 atm of hydrogen gas, further hydrogenation does not produce the complex [P2N2]TaH3; instead, reduction of the tantalum center occurs to yield the dinuclear Ta(IV) hydride ([P2N2]Ta)(2)-(mu-H)(4). This diamagnetic tetrahydride fails to react with many reagents, including ethylene and carbon monoxide; however, upon addition of iodomethane, {([P2N2]Ta)(2)(mu-H)(4)}I-+(-) is produced as a paramagnetic green crystalline solid. The number of hydrides in this reaction product was confirmed by a deuterium labeling study. The results of a variable-temperature magnetic susceptibility study of this tetrahydride cation can be partially modeled with the Curie-Weiss law and a large correction for temperature-independent magnetism. Ab initio calculations using density functional theory were performed in an attempt to further understand the influence of the macrocyclic ligand in the bonding in these complexes.