The Br and I analogues of ReCl(H < inf> 2 )(PMePh < inf> 2 ) < inf> 4 ; crystal structures of ReBR(H < inf> 2 )(PMePh < inf> 2 ) < inf> 4 and the [ReO < inf> 2 (Py) < inf> 4 ] < sup> + cation; possible solution state evidence of Re-H···H···N(Py) interactions as evident in T < inf> 1 measurements

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The syntheses of the Br and I analogues of ReCl(H2)(PMePh2)4 are reported together with their characterizations by NMR, and in the case of the Br analogue, FABMS and a single crystal X-ray diffraction study. The minimum T1, for the metal bonded hydrogen atoms in the Br and I analogues was determined to be 62 and 101 ms at 400 MHz, respectively. A decrease of 9 ms in the room temperature T1 measurement of ReCl(H2)(PMePh2)4 was observed upon addition of pyridine to the NMR tube. This is suggestive of an interaction between the dihydrogen ligand and the lone pair of electrons on the N-atom in py. The crystal structure of ReBr(H2)(PMePh2)4 revealed that the structure consisted of a trans dihydrogen to halide arrangement and was disordered with respect to the locations of the dihydrogen ligand and the halide in the crystal. The crystal structure of the trans-[ReO2(Py)4]+ cation is also reported. © 2001 Elsevier Science Ltd. All rights reserved.

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