Pseudo-raft rhenium–platinum clusters. Synthesis and crystal structure of the anions [PtRe₃(µ-H)(CO)₁₃]^2–and [PtRe₄(CO)₁₇]^2–, containing a central Pt atom surrounded by a folded stripe of Re atoms

Abstract

The redox condensation between [{Pt,(CO),},]2-(n z 10) and rhenium carbonyl anions gives two novel mixed-metal species, [PtRe,(p-H)(C0),J2-and [PtRe,(C0),J2-, containing a Pt-CO unit interacting with three and four Re(CO), moieties, respectively, arranged as a stripe folded around the Pt atom and whose formation confirms the tendency of Re atoms t o cluster around Pt, giving structures based on Re,Pt triangles with a low Pt: Re ratio.

Unsaturated Platinum−Rhenium Cluster Complexes. Synthesis, Structures and Reactivity

“…The metal cluster is structurally similar to the platinum−rhenium dianion, [PtRe 3 (CO) 13 (μ-H)] 2- , 16 , obtained by Beringhelli et al from the reaction of [{Pt 3 (CO) 6 } n ] 2- with [Re 2 (CO) 8 H 2 (μ-H)] - . The hydride bridged Pt−Re bond in 16 is 2.799(1) Å in length.…”

A pseudo-trigonal bipyramidally coordinated Pt atom in dicarbonylbis(octacarbonyl-μ-dicyclohexylphosphidodirhenio)platinum(II)

“…The Re1ÐRe2 bond is 3.2620 (15) A Ê and the "-P1 bridge is symmetric with respect to the equivalent PÐRe bond lengths of 2.454 (6) and 2.459 (6) A Ê . The two PtÐRe bonds differ slightly in length [2.9165 (12) and 2.9025 (15) A Ê for Re1 and Re2, respectively], but they are longer than other unsupported PtÐRe bonds reported in the literature, which range from 2.706 (1) to 2.899 (1) A Ê (Casey et al, 1987(Casey et al, , 1992Urbancic et al, 1984;Beringhelli et al, 1990Beringhelli et al, , 1993Mague & Lin, 1994). A "-H bridged PtÐRe edge has been reported with a length of 2.906 (1) A Ê (Beringhelli et al, 1990).…”

Binary Carbonyls, Carbonyls plus Hydrides, Carbonyls plus Phosphines, Cyclic Hydrocarbyls and Main-group Ligands without Acyclic Hydrocarbyls

“…The H O M O in the anionic clusters is a a* o r b i t a l which is antibonding between the c e n t r a l p l a t i n u m atoms, b u t essentially nonbonding between the platinum a n d i r o n atoms. 9 9 ' 1 0 0 Several other heteroplatinum clusters have p l a n a r or puckered r a f t s t r u c t u r e s based on fused triangles, namely [Re 4 Pt(CO) 1 7 ] 2~ (8), 27 [Os 3 Pt 2 (CO) 14 ] (9) 72 a n d [M 4 Pt 2 (CO) 1 8 ] ( M = Ru 6 7 ' 6 9 o r Os 7 3 ' 7 6 ) (10). The s t r u c t u r e s of (9) a n d (10) a r e shown in Figure 1 .…”

“…The 'archetypal' structure is that o f (26), and cluster (28) is closely related, with a 14-electron Pt(CO) 2 vertex replacing a 16-electron Os(CO) 3 H 2 vertex. Cluster (27) is formally derived by removal of an Os(CO) 2 H 2 vertex f r o m (26), with one CO ligand transferring to a remaining osmium atom. Cluster (31) has a similar metal skeleton to (27), resulting f r o m the formal removal of an OsH 4 group.…”

“…Cluster (27) is formally derived by removal of an Os(CO) 2 H 2 vertex f r o m (26), with one CO ligand transferring to a remaining osmium atom. Cluster (31) has a similar metal skeleton to (27), resulting f r o m the formal removal of an OsH 4 group. A carbonyl ligand has been transferred to the platinum atom and there is a reorientation of the hydrides.…”