The capture of dioxygen, carbon monoxide and sulfur dioxide by [(PMe2Ph)4Pt2B10H10].
The metal-metal bond in [(PMe2Ph)4Pt2B10H10], from reaction of [PtCl2(PMe2Ph)2] or PMe2Ph with [(PMe2Ph)2PtB10H12], very readily, and readily reversibly, takes up atmospheric O2 to give the peroxidic dioxygen-dimetallaborane complex [(PMe2Ph)4(O2)Pt2B10H10], which has Pt-Pt 2.7143(3), Pt-O 2.141(4) and 2.151(4), and O-O 1.434(6)A. The {Pt2O2} bonding mode is fluxional. Compound irreversibly takes up CO to give the bridging-carbonyl-dimetallaborane complex [(PMe2Ph)4(CO)Pt2B10H10] which has a CO vector radial to the cluster, with Pt-Pt 2.7488(3), Pt-C 2.104(6) and 2.113(6), and C-O 1.163(6)A; CO readily displaces O2 from to give 3. SO2 similarly reacts with either or to give [(PMe2Ph)4(SO2)Pt2B10H10], which has tetrahedral sulfur, with Pt-Pt 2.8194(4), Pt-S 2.350(2) and 2.381(3), and S-O 1.470(8)A and 1.477(9)A.
Bould
Jonathan
J
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK. bould@chem.leeds.ac.uk
Kilner
Colin A
CA
Kennedy
John D
JD