Complexes of Ir₃(CO)₃(η⁵-C₉H₇)₃with Metal Fragment Electrophiles

Abstract

The reactions of C 3 v Ir3(μ-CO)3(η5-C9H7)3 (1) with various metal electrophiles yield the cationic tetranuclear clusters [Ir3{M(PPh3)}(CO)3(η5-C9H7)3][PF6] (2, M = Cu; 3, M = Ag; 5, M = Au), [Ir3Tl(μ-CO)3(η5-C9H7)3][PF6] (4), and [Ir3(HgR)(CO)3(η5-C9H7)3][PF6] (6, R = Ph; 7, R = W(CO)3(η5-C5H5)). Compounds 5−7 are best prepared via compound 4. The structures of compounds 4 and 5 have been determined by X-ray diffraction. The C 3 v symmetry of the parent cluster 1 is maintained in the structure of 4. The molecule consists of a triangle of iridium atoms, each edge of which has a bridging carbonyl oriented out of the plane in the same direction and each vertex of which has an η5-indenyl ligand oriented toward the opposite side of the plane. The thallium atom adopts a face-capping mode of coordination on the same side of the triiridium plane as the three indenyl ligands and is encapsulated by the phenylene portions of the indenyl groups. The molecular structure of 5 consists of a AuIr3 butterfly framework with a hinge angle of 153.63(3)° and the gold atom in a wingtip position. Each CO ligand is bonded in a terminal mode to one iridium center, with one CO ligand ‘down' relative to the Ir3 plane and two CO ligands ‘up', flanking the Ir−Ir edge bridged by the Au(PPh3)+ fragment. The indenyl ligands take up positions opposite those of the CO ligands at each iridium center. The infrared and 1H NMR spectra of compounds 2, 3, 5, 6, and 7 are all very similar and are fully consistent with the solid-state structure of 5.

Hierarchical nanosheets built from superatomic clusters: properties, exfoliation and single-crystal-to-single-crystal intercalation

“…For example, treating the (a,a,a) isomer of the indenyl complex Ir 3 (CO) 3 (h 5 -C 9 H 7 ) 3 with the electrophile [Au(PPh 3 )][PF 6 ] allows the isolation of the (a,a,b) isomer as the {Ir 3 [Au(PPh 3 )](CO) 3 (h 5 -C 9 H 7 ) 3 }[PF 6 ] adduct. 39 While different structural phases of the same elemental composition are prevalent in both extended and molecular inorganic materials, such well-dened, localized isomerism is typically associated with organic structures; 1 represents an unusual and rare example of stereoisomerism within a well-dened inorganic cluster core. [40][41][42] Investigating the origin of the stereoselectivity guiding the interaction of the edge Co with the Co 6 Se 8 surface in 1, we note an analogy with how metal adatoms discriminate between different surface sites of inorganic supports, preferentially adsorbing to minimize adsorption-induced strain.…”

Iridium–Gold Cluster Compounds: Syntheses, Structures, and an Unusual Ligand-Induced Skeletal Rearrangement

“…Combining transition metals with gold has led to interesting new bimetallic catalysts for the oxidation of hydrocarbons . There have been very few reports of iridium–gold carbonyl cluster complexes, , and their catalytic activity has not yet been investigated.…”

Extended structures containing Pt(ii)–Tl(i) bonds. Effect of these interactions on the luminescence of cyclometalated Pt(ii) compounds

“…Probably due to favourable contribution of relativistic effects most of them involve third row metals such as Pt(II) [30][31][32][33][34][35][36][37][38][39][40][41][42][43] and Ir(I). [44][45][46] A few examples with the counterparts second row metal ions Pd(II) 47, 48 and Rh(I) 49 and more recently the crystal structure of the related Tl 2 Ni(CN) 4 47 have also appeared. In the case of platinum considerable experimental work and theoretical calculations 34,47,50,51 have shown that the strength of the metallophilic Pt II -Tl I interaction depends on the nature of the platinum substrate.…”