An unusual example of intramolecular hydrogen bonding in a metal carbonyl cluster compound. Synthesis and crystal and molecular structure of di-.mu.-carbonylhexadecacarbonyldi-.mu.-hydroxo-.mu.4-sulfidohexaruthenium

Abstract

and others6 shows that fluorocarbon complexation, although weak, may be a common phenomenon in the coordination chemistry of fluorocarbons, at least for coordinatively unsaturated metal centers. The 19F coordination shift and, in suitable cases, the observation (21) Cromer, D.

Reactivity of a Cationic Non-Hydridic Triruthenium Carbonyl Cluster Complex with Anionic Reagents. Synthesis of New Tri- and Hexanuclear Derivatives

“…In contrast, cluster 6 is electron precise (the sulfur atom contributes four electrons to the cluster). This is reflected by the Ru−Ru distances associated with the capping sulfur atom: while the tetragons of the 94-electron compounds contain two Ru−Ru distances longer than the other two and longer than those expected for normal Ru−Ru bonds (average values 3.014(1), 3.076(1), and 3.156(3) Å for [Ru 6 (μ 4 -S)(μ-OH) 2 (CO) 18 ], [Ru 6 (μ-SH)(μ 4 -S)(μ 3 -Spy)(CO) 17 ], and [Ru 6 (μ 4 -S)(μ 3 -RNCNHR)(μ 3 -RNCSNHR)(CO) 16 ], respectively) the tetragon of compound 6 is nearly regular, with the four Ru−Ru bond distances ranging from 2.868(2) to 2.911(2) Å.…”

“…Other structurally related hexaruthenium carbonyl cluster compounds containing μ 4 -S ligands are known, namely, [Ru 6 (μ 4 -S)(μ-OH) 2 (CO) 18 ], [Ru 6 (μ-SH)(μ 4 -S)(μ 3 -Spy)(CO) 17 ] (HSpy = pyridine-2-thiol), and [Ru 6 (μ 4 -S)(μ 3 -RNCNHR)(μ 3 -RNCSNHR)(CO) 16 ] (R = Ph, Et) …”

Structurally Characterized Organometallic Hydroxo Complexes of the f- and d-Block Metals

“…Two lowenergy absorptions which are responsible for the compound's blue color are attributed to the extra two electrons occupying antibonding orbitals within the core of the molecule. 84 A final Mg complex is [Ru3Cl3(CO)g(COEt)2(^i3-OH)]2. 85 The three ruthenium atoms in each half of the dimeric unit are octahedrally coordinated.…”

New Water-Soluble Ruthenium(II) and Osmium(II) Hydroxo Carbonyl Complexes

“…Thus, [Rh(1,5-COD)(OH)] 2 ,4a [Rh(PPh 3 ) 2 (OH)] 2 ,4b and [Rh(CO)(PPh 3 ) 2 (OH)] 4c are known but the related [Rh(CO) 2 (OH)] 2 is not stable enough, in contrast to [Rh(CO) 2 (OR)] 2 (R = Me,5a Ph,5a SiPh 3 5b ). Similarly, whereas hydroxo complexes of ruthenium(II) and osmium(II) with phosphines, , cyclopentadiene, or arenes 6,9 as ligands are known, no simple hydroxoruthenium(II) or -osmium(II) carbonyl complexes have been reported, with the exception of some hydroxoruthenium and -osmium carbonyl clusters. ,, The only related Os(II) compounds are the oxocarbonyl species [Os 4 O 4 (CO) 12 ] and [Os 6 O 6 (CO) 16 ], obtained as byproducts of the carbonylation of OsO 4 to [Os 3 (CO) 12 ] …”