Synthesis and molecular structures of tris(thio- and selenophenyl)stannyl complexes of cyclopentadienylcarbonylnitrosylmanganese and their reaction products with tungsten carbony

Reactions of CpMn(CO)(NO)SnCl ₃ (I) with sodium benzenethiolate and sodium benzenesele-nolate gave orange crystals of the complexes CpMn(CO)(NO)Sn(EPh) ₃, where E = S (II) or Se (III). Treatment of complex II with photochemically generated W(CO) ₅(THF) yielded the adduct CpMn(CO)(NO)Sn(SPh) ₃ • W(CO) ₅ (IV). A similar treatment of complex III resulted in the formation of the ditungsten complex W ₂(CO) ₄(SePh) ₆ (V) with transfer of all chalcogenate groups from tin to tungsten. In reactions of complexes II and III with a Pt ₀ complex with phosphine and acetylene, (PPh ₃) ₂Pt(Ph ₂C ₂), the chalcogenate groups are transferred from tin. Only the known Pt(II) complexes (PPh ₃) ₂Pt(EPh) ₂), where E= S (VI) or Se (VII). Molecular structures IV and V were characterized by X-ray diffraction. It has been found that the Mn-Sn bond in complex IV (2.5479(9) Å) is nearly the same length as that found earlier for complex II (2.5328(17) Å) and is substantially shorter than the sum of the covalent radii of Mn and Sn (2.78 Å). The Sn-S bond is noticeably lengthened (2.5217(11) Å) only for the S atom bound to tungsten (W-S, 2.5696(12) Å), while the other Sn-S bonds (2.4413(12) and 2.4291(12) Å) are virtually the same as in complex II (on average, 2.441 Å). Complex V contains the direct W-W bond (2.8153(16) Å) supplemented with four benzeneselenolate bridges in which the W-Se bonds (on average, 2.642(2) Å) are longer than the two terminal W-SePh bonds (2.571(2) Å). All the W-Se bonds are much shorter than the sum of the covalent radii of W and Se (2.82 Å).