Improved syntheses of M[Fe2(CO)8]2 (M = Si, Ge or Sn) and the X-ray crystal structure of Si[Fe2(CO)8]2

Transformations in Transition-Metal Carbonyls Containing Arsenic: Exploring the Chemistry of [Et4N]2[HAs{Fe(CO)4}3] in the Search for Single-Source Precursors for Advanced Metal Pnictide Materials

“…X is a neutral molecule and obeys the 18-electron rule. The average M–M bond is 2.821(25) Å, similar to 2.816(44) Å, the average M–M bond distance for a variety of spirocyclic EM 2 (CO) 8 compounds where M were first-row transition metals. ,− It was also similar to the 2.8191(15) Å observed in [ VII ] − . Table gives a comparison of X to all known E­{Fe 2 (CO) 8 } 2 clusters where E is a main-group atom (E = Si, Ge, In, Sn, Pb).…”

“…The CO-bridged Fe–Fe bond is short at 2.6051(18) Å, although it is consistent with the other known examples of an {Fe 2 (CO) 7 H} group (average 2.585(15) Å including that of [ IV ] − ). − The Fe–Mn bond is much longer at 2.8191(15) Å, though consistent with other M–M bonds in M 2 (CO) 8 spirocyclic environments (average 2.816(44) Å). ,− The average arsenic bond distance to the {Fe 2 (CO) 7 H} fragment is 2.377(6) Å, while the As–Fe/Mn distances are slightly shorter at 2.3647(2) Å, likely due to less strain in the FeMn­(CO) 8 moiety. The bond distance of the CO bond in the bridging carbonyl (C120–O120) of 1.132(4) Å appears to be shorter than the respective bridging carbonyls of the other known {Fe 2 (CO) 7 H} groups (average of 1.182(12) Å). − …”

“…[ VII ] − and X belong to a general class of metal carbonyl clusters in which two M 2 units, each containing a metal–metal bond, are bound to a central main-group atom, a well-known configuration (Figure ). − Both [ VII ] − and X contain three Fe atoms and one Mn atom divided between two M 2 fragments (Figures and ). [ VII ] − and X each possess an MnFe­(CO) 8 fragment as well as a diiron unit which is (μ-H)­Fe 2 (CO) 6 (μ-CO) − and Fe 2 (CO) 8 for [ VII ] − and X , respectively.…”

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

“…Complexes containing a SiH 3 substituent are rare and the early examples were prepared by salt elimination between H 3 SiX and L n M - . 2a,b Silyl complexes derived from SiH 4 or a precursor that generates SiH 4 are shown in Table . − Probably the difficulty of handling SiH 4 discourages many investigators from studying its reactivity. However, problems also arise due to additional transformations that occur at Si−H bonds in the initially formed TM−SiH 3 complex which lead to product mixtures or insoluble materials that are difficult to characterize.…”

Polyhedral and Spiro Platinum−Silyl Clusters Bearing Phosphine Ligands

“…In the crystal structure (Figure ), the two Pt 2 (μ-dppe) units with a Pt−Pt single bond are bridged by two dppe ligands and the tetragonal structural μ 4 -silicon atom. The M−M bond lengths are 2.69 Å and are shorter than that of [Fe 4 (CO) 16 (μ 4 -Si)] (2.79 Å) without a bridging ligand, despite the presence of the third row transition metal Pt, which causes the geometry of the silicon atoms to be distorted relative to organosilicon compounds such as the spiro-type bisilafluorene . The sum of the bond angles around the Pt centers is almost 360°, indicating that the platinum atoms have planar geometries.…”