The preparation of some manganese–mercury cluster complexes and a study of their redistribution reactions

Abstract

The heterometallic cluster complexes [ Mn,(p-H g Ph) (p-PPh,) (CO) (3), and [Hg{Mn,(p-PPh2)(CO)8)2] (4) have been prepared by reaction of [N( PPh,)2][Mn2(p-PPh2)(CO)8] (1) with, respectively, HgPhCI, HgCI,, and Hg(CN),. Some redistribution reactions of (2), (3), and (4) (in which the Hg atom is three-or four-co-ordinate) have been investigated and are compared with previously studied redistribution reactions of transition-metal-mercury complexes containing two-co-ordinate mercury atoms.

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

“…The 31 P NMR spectra of these compounds (Table 1) exhibit quite deshielded phosphide resonances (as invariably found for our triply-bonded dimolybdenum complexes) displaying 199 Hg couplings of 268 Hz (9) and 198 Hz (10), thus confirming the presence of Hg atoms bound to the dimolybdenum centres. For instance, the P-Hg coupling in the related (if electron-precise) heterometallic cluster [Mn 2 (l-HgCl)(l-PPh 2 )(CO) 8 ] was found to be 258 Hz [27].…”

“…This compound, quite insoluble in most of the organic solvents, could be only characterized spectroscopically, since crystals suitable for an X-ray analysis could not be grown. The structure proposed for 8 is based on those of previously reported clusters having M 4 Hg skeletons, such as [Fe 2 {l-C@CH-(CH 2 OCH 3 )}(l-S t Bu)(CO) 6 [27], a cluster found to be also very insoluble in organic solvents. In all these compounds, the metal atoms around the Hg atom define a pseudotetrahedral geometry, although the angles formed by the two ''M 2 Hg" triangles can be quite different from 90°, depending on quite subtle factors.…”

Manganese Alkyls and Hydrides

“…Alkynes RC=CR (R = H, CF 3 , or Ph) readily insert into the Mn-H bond of (282) (entry 16, Table 7; L = CO) to form complexes (285) in yields of 46-99%. 267 In addition, dihydride (273) (entry 5, Table 7) inserts acetaldehyde or methylisonitrile generating u-ethoxide complex (274) (entry 6) or bridged imine (275) (entry 7), respectively. 261 Ethyne readily inserts into the Mn-H bond in (272a) (entry 1 , Table 7) to form the bridged vinyl species (276) (entry 8), and Equation (75) illustrates the insertion of f-butylacetylene into (272a) to form (277) and (286).…”

“…270 Photolysis or heating of (282) (entry 16, L = CO) in the presence of potential ligands yields (282) where L is any of a variety of phosphines, phosphites, isonitriles, and so on. 267 Resonance Raman and IR spectra of various hydrogen-deuterium isotopomers of Mn 3 H 3 (CO) 12 have been reported. 273 ' 274 2 .…”

Cluster Complexes with Bonds Between Transition Elements and Copper, Silver and Gold

“…(i) Clusters in which the metals are only ligated by organophosphine groups and hydrido ligands, for example, [Cu 2 Re 4 H, 4 (PMe 2 Ph) 8 ] , 314 [ A g 3 R h 3 ( j L i -H ) 9 321 The chemistry o f these very large clusters is discussed in detail in References 313 and 322. In the vast majority of the group 1 1 metal heteronuclear clusters reported so far, one simple neutral two-electron donor ligand is attached to each coinage metal and PR 3 ( R = alkyl or aryl) is by f a r the most common ligand of this type.…”