High yield synthesis, molecular structure, and reactions of the 16-electron norbornadiene complex, [WI2(CO)2(nbd)]

Article abstract of DOI:10.1002/1521-3749(200208)628:8<1727::AID-ZAAC1727>3.0.CO;2-A

Reaction of equimolar amounts of [WI₂(CO)₃(NCMe)₂] and norbornadiene (nbd) in toluene at 95°C for 3h gave the 16-electron crystallographically characterised complex, [WI₂(CO)₂(nbd)] (1) in 96% yield. The structure of 1 has a distorted octahedral geometry, with the two cis- iodo ligands opposite to the two alkene groups in the equatorial plane, with the carbonyl groups in the axial sites. Treatment of 1 with two equivalents of PhC₂Ph in CH₂Cl₂ at room temperature afforded the bis(alkyne) complex [WI₂(CO)₂(η²-PhC₂Ph) ₂] (2). Equimolar quantities of 1 and 4,4′-bipyridine react in CH₂Cl₂ at room temperature to yield the seven-coordinate complex, [WI₂(CO)₂(4,4′-bipyridine)(nbd)] (3).