title: Macropolyhedral boron-containing cluster chemistry. Ligand-induced two-electron variations of intercluster bonding intimacy. Structures of nineteen-vertex [(eta5-C5Me5)HIrB18H19(PMe2Ph)] and the related carbene complex [(eta5-C5Me5)HIrB18H19[C(NHMe)2]].
abstract: Addition of PMe2Ph to fused-cluster syn-[(eta5-C5Me5)IrB18H20] 1 to give [(eta5-C5Me5)HIrB18H19(PMe2Ph)] 3 entails a diminution in the degree of intimacy of the intercluster fusion, rather than retention of inter-subcluster binding intimacy and a nido-->arachno conversion of the character of either of the subclusters. Reaction with MeNC gives [(eta5-C5Me5)HIrB18H19[C(NHMe)2]] 4 which has a similar structure, but with the ligand now being the carbene [:C(NHMe)2], resulting from a reductive assembly reaction involving two MeNC residues and the loss of a carbon atom.
authors.affiliation: The School of Chemistry of the University of Leeds, Leeds, UK LS2 9JT.
authors.forename: Suzanne L
authors.initials: SL
authors.lastname: Shea
authors.forename: Tomás
authors.initials: T
authors.lastname: Jelínek
authors.forename: Sarath D
authors.initials: SD
authors.lastname: Perera
authors.forename: Bohumil
authors.initials: B
authors.lastname: Stíbr
authors.forename: Mark
authors.initials: M
authors.lastname: Thornton-Pett
authors.forename: John D
authors.initials: JD
authors.lastname: Kennedy