Coordinatively unsaturated complexes [M-2(CO)(4)(mu-H)(mu-(PBu2)-Bu-t)-(mu-Ph2PCH2PPh2)] (M=Fe, Ru): synthesis and crystal structures of [Fe-2(CO)(4)(mu-H)(mu-SO)(mu-(PBu2)-Bu-t)(mu-Ph2PCH2PPh2)] and [Ru-2(CO)(4)(mu-H)(mu-SO2)(mu-(PBu2)-Bu-t)(mu-Ph2P

摘要

Fe-2(CO)(4)(mu-H)(mu-(PBu2)-Bu-t)(mu-dppm)] (1a) reacts with elemental sulfur to give [Fe-2(CO)(4)(mu-H)(mu-S)(mu-(PBu2)-Bu-t)(mu-dppm)] (2a) (dppm=Ph2PCH2PPh2). The reaction of 1a with CCl4 or CHCl3 affords spontaneously in nearly quantitative yield [Fe-2(CO)(4)(mu-Cl)(mu-(PBu2)-Bu-t)(mu-dppm)] (3a). [Ru-2(CO)(4)(mu-H)(mu-(PBu2)-Bu-t)(mu-dppm)] (1b) reacts with SO2 in THF under normal conditions to [Ru-2(CO)(4)(mu-H)(mu-SO2)(mu-(PBu2)-Bu-t)(mu-dppm)] (5b). 5b is also formed by oxidation of the sulfido ligand in [Ru-2(CO)(4)(mu-H)(mu-S)(mu-(PBu2)-Bu-t)(mu-dppm)] (2b) by means of 3-chloroperoxybenzoic acid or H2O2 as oxidizing reagent. As the primary oxidation products of 2a or 2b the sulfur monoxide complexes [M-2(CO)(4)(mu-H)(mu-SO)(mu-(PBu2)-Bu-t)(mu-dppm)] (M=Fe, 4a; M=Ru, 4b) are obtained by using 3-phenyl-2-(phenylsulfonyl)-oxaziridine as oxidizing reagent. The molecular structures of 4a and 5b were confirmed by crystal structure analyses. (C) 2003 Elsevier Science B.V. All rights reserved. [References: 23