Synthesis and Structure of Two New High Nuclearity Ru/Pt Mixed‐Metal Clusters

Cage Rearrangements in Dodecanuclear Co–Pt Dicarbido Clusters Promoted by Redox Reactions

“…[10] Thus, it is composed of three face-sharing octahedra, the external ones being centred by two C atoms. [14] According to the condensed polyhedral approach proposed by Mingos, [19] a three-face-sharing-octahedra cluster should have 162 CVE. The composition of the crystal has been independently determined by ESI-MS, elemental analyses and free refinement of the crystallographic data, giving very similar results.…”

“…Several examples of dodecanuclear M 12 E 2 (E = C, N) MCCs containing two interstitial isolated heteroatoms are known, i.e. [ 1 ] 2– , [ 2 ] 4– , [ 3 ] 4– , [ 4 ] 2– , [Rh 12 C 2 (CO) 24 ] 2– ,11 [Rh 12 C 2 (CO) 23 ] 4– ,11 [Rh 12 C 2 (CO) 24 (AuPPh 3 )] – ,12 [HRh 12 N 2 (CO) 23 ] 3– ,13 [Ru 10 Pt 2 C 2 (CO) 28 ] 2– ,14 [Co 10 Rh 2 N 2 (CO) 24 ] 2– ,15 [Co 11 RhN 2 (CO) 24 ] 2–[15] and [Fe 6 Ni 6 N 2 (CO) 24 ] n – ( n = 2–4) 16. As far as we are aware, only two examples are known of M 12 E 2 (E = C, N) MCCs containing a direct E–E bond, i.e.…”

“…The number of CVE for these species is 168–170, and all of them are reported to be multivalent. Also, [Ru 10 Pt 2 C 2 (CO) 28 ] 2– (166 CVE) is based on three edge‐sharing octahedra with the two common edges missing (Figure 4b) 14. According to the condensed polyhedral approach proposed by Mingos,19 a three‐face‐sharing‐octahedra cluster should have 162 CVE.…”

“…Each interstitial carbide atom has a coordination number of eight and displays six C-Co and two C-Pt contacts. ESI-MS analyses on the same crystals indicate that this composition corresponds to a mixture of the species [Co 8 Pt 4 C 2 (CO) 24 [11] [Rh 12 C 2 (CO) 23 ] 4-, [11] [Rh 12 C 2 (CO) 24 (AuPPh 3 )] -, [12] [HRh 12 -N 2 (CO) 23 ] 3-, [13] [Ru 10 Pt 2 C 2 (CO) 28 ] 2-, [14] [Co 10 Rh 2 N 2 -(CO) 24 ] 2-, [15] [Co 11 RhN 2 (CO) 24 ] 2- [15] and [Fe 6 Ni 6 N 2 -(CO) 24 ] n-(n = 2-4). The interlayer M-M bonds are not supported by bridging ligands.…”

Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru6(CO)16]2−[Pt2(CO)2(dppm)2]2+ion pair on the way to [Ru6C(CO)16Pt3(dppm)2]

“…10, 12 The number of reported Pt-Ru clusters with more than six metal atoms in their frameworks is still limited. [13][14][15][16][17][18][19][20] Moreover, most of them were obtained in low yield as minor products of nondirected synthetic processes. These reasons prompted us to search for novel routs to mixed metal Ru containing clusters on the basis of synthetic approaches successfully applied earlier for the preparation of platinum-rhodium clusters.…”