Carbidoheptarhenate Cluster Complexes of Mercury with Hydrosulfide or Functionalized Thiolate Ligands

Abstract

The hydroxo complex [Re7C(CO)21HgOH]2- reacts at room temperature with H2S to give the hydrosulfide complex [Re7C(CO)21HgSH]2- and with various thiols HS-Z to give the derivatives [Re7C(CO)21HgS-Z]2-, where Z contains a free amine or carboxyl group.

Carbidoheptarhenate Cluster Complexes of Cadmium and Zinc Units: The Structure of [PPh4]2[Re7C(CO)21(μ3-ZnCl)]

“…It contains an octahedron of rhenium atoms, centered on an interstitial carbon atom, with rhenium tricarbonyl and zinc chloride units capping trans (1,4) faces. This is the characteristic geometry found previously for carbidoheptarhenate complexes, , in particular, the mercury-capped dervivatives. − The average Re−Re distances for the zinc-capped face in 2 are ca. 0.05 Å longer than those for the uncapped faces, which average 2.98 Å.…”

“…2.88 Å in the corresponding mercury derivatives. [1][2][3] The implied difference in covalent radius is similar to that suggested by comparing M-N distances in four-coordinate (11) This characteristic IR band of carbidoheptarhenate complexes is extremely intense. The molar absorption coefficient directly determined for the HgCl complex is 7.0 × 10 4 cm -1 M -1 , and the analogous best fit parameter for the ZnCl complex 2 is 5.3 × 10 pyrazolylborate complexes of mercury (ca.…”

“…This is the characteristic geometry found previously for carbidoheptarhenate complexes, 15,16 in particular, the mercury-capped dervivatives. [1][2][3] The average Re-Re distances for the zinc-capped face in 2 are ca. 0.05 Å longer than those for the uncapped faces, which average 2.98 Å.…”

“…As part of our investigation of carbidoheptarhenate cluster complexes of mercury units, with the general formula [Re 7 C-(CO) 21 (µ 3 -HgX)] 2-, [1][2][3][4] we became interested in extending this chemistry to include the lighter group 12 congeners, namely, cadmium and zinc. A recent discussion of cluster complexes with various bonds between transition elements and zinc, cadmium, or mercury is available.…”

Rhodium and Iridium Hydroxide Complexes [M(μ-OH)(COD)]2(M = Rh, Ir) as Versatile Precursors of Homo and Early−Late Heterobimetallic Compounds. X-ray Crystal Structures of Cp*Ta(μ3-O)4[Rh(COD)]4(Cp* = η5-C5Me5) and [Ir(2-O-3-CN-4,6-Me2-C5HN)(COD)]2

“…A great deal of attention has been paid lately to the broad family of hydroxo metal “M−OH” complexes, which are either monomeric, dimeric, or polymeric, due to the interesting reactivity and potential relevance to catalytic reactions . Such complexes can react with protic electrophiles (HX), releasing water and leading to the formation of new M−X bonds, they can act asproton-transfer agents (Brönsted acid), producing heterometallic oxo (M−OH + M‘−R → M−O−M‘) or carboxylato complexes [(M−OH + M‘−CO + → M‘M 2 -(μ 3 CO 2 )], or as Brönsted bases with hydroxide/alkoxide exchange, or they may use their nucleophilic properties, allowing the synthesis of a wide variety of new complexes . The hydroxide ion can also act as a one-electron reducing agent …”